Extraction of target materials using czts sorbent

ABSTRACT

Various embodiments disclosed relate to extraction of target materials using a CZTS sorbent. A method of extracting a target material from a medium includes contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium including the target material to form a used CZTS sorbent that includes the target material. The method also includes separating the used CZTS sorbent from the medium.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of and claims the benefit ofpriority under 35 U.S.C. § 120 to U.S. Utility application Ser. No.16/042,840 filed Jul. 23, 2018, which is a continuation-in-part of U.S.patent application Ser. No. 15/606,704, filed on May 26, 2017, which isa continuation-in-part of U.S. patent application Ser. No. 14/808,563,filed on Jul. 24, 2015, which claims the benefit of U.S. ProvisionalApplication No. 62/029,044, filed Jul. 25, 2014 and U.S. ProvisionalApplication No. 62/133,791, filed Mar. 16, 2015, the disclosures ofwhich are incorporated herein in their entirety by reference.

BACKGROUND

This section provides background information related to the presentdisclosure which is not necessarily prior art.

Many industries from numerous sectors of the economy have emissions ofone kind or another. Such emissions can be separated into two basicgroups, one being gaseous and the other being non-gaseous. It is commonfor emissions in the gaseous group and emissions in the non-gaseousgroup to contain hazardous contaminants. Emissions in the gaseous groupmay be in the form of exhaust gases generated by a coal fired plant orfrom a natural gas burning facility. Emissions in the non-gaseous groupmay be in the form of liquid-like, sludge-like, or slurry-likesubstances. If and when the level of hazardous contaminants in emissionsmeets and/or exceeds allowable limits, the contaminants must either beneutralized, captured, collected, removed, disposed of, and/or properlycontained by one means or another.

Many industries rely upon burning a fuel material as a means toaccomplish some aspect of their respective process. For instance, in afirst example, steel mills burn and/or smelt metal in the process ofmaking metal shapes, extrusions, and other metal castings. The processesused in the metal industry include operations in which particulates areemitted in metallic vapor and ionized metal. Hazardous contaminants tothe environment, plants, animals, and/or humans are released into theair via the metallic vapor. To one degree or another, the hazardouscontaminants in the metallic vapor and/or the metallic vapor compoundsmust be collected and disposed of properly. In a second example, theindustry of mining precious heavy metals such as gold, silver, andplatinum includes metals and metallic vapor emissions containing heavymetal contaminants and particulates that are considered hazardous if notcaptured, collected, and disposed of properly. In a third example,industries burning natural gas have emissions that often containelevated levels of contaminants that are considered to be hazardous ifnot captured, collected, and disposed of properly. In a fourth example,the producers of energy who use coal as a burnable consumable to createsteam in boilers for turning generators have considerable emissionscontaining metallic vapor and metallic compounds that are consideredhazardous to the environment, plants, animals, and humans. Among otherhazardous contaminants, metallic vapor emissions often contain mercury(Hg).

Because of the pattern of global jet streams, airborne metallic vaporemissions may be carried from one country and deposited in another. Forinstance, it is possible that much of the emissions of mercury generatedin China and/or India may actually end up being deposited in the USAand/or the ocean waters in between. In a similar fashion, much of themercury laden emissions generated in the USA may actually be depositedin Europe and/or in the ocean waters in between. To complete thiscircle, much of the mercury laden emissions generated in Europe mayactually be deposited in China and/or India. Therefore, the containmentof mercury and other hazardous contaminants in emissions generated byindustrial processes is a global problem with global implicationsrequiring a global effort to resolve it.

National and international regulations, rules, restrictions, fees,monitoring, and a long line of ever evolving and increasingly stringentlaws are proposed and/or enforced upon those generating such emissions.For example, one of the most egregious and regulated contaminants inmetallic vapor emissions is mercury. Human industrial processes havegreatly increased the accumulation of mercury and/or mercury deposits inconcentrations that are well above naturally occurring levels. On aglobal basis, it is estimated that the total quantity of mercuryreleased by human-based activities is as much as 1,960 metric tons peryear. This figure was calculated from data analyzed in 2010. Worldwide,the largest contributors to this particular type of emission are coalburning (24%) and gold mining (37%) activities. In the USA, coal burningaccounts for a higher percentage of emissions than gold miningactivities.

The primary problem with exposure to mercury for animals and humans isthat it is a bioaccumulation substance. Therefore, any amount of mercuryingested by fish or other animals remains in the animal (i.e.accumulates) and is passed on to humans or other animals when the formeris ingested by the later. Furthermore, the mercury is never excretedfrom the body of the ingesting host. In the food chain, largerpredators, which either live the longest and/or eat large quantities ofother animals, are at the greatest risk of having excessive mercuryaccumulations. Humans, who eat too much mercury-laden animals,especially fish, are subject to a wide range of well-known medicalissues including nervous system maladies and/or reproductive problems.

There are three primary types of mercury emissions: anthropogenicemissions, re-emission, and naturally occurring emissions. Anthropogenicemissions are mostly the result of industrial activity. Anthropogenicemission sources include industrial coal burning plants, natural gasburning facilities, cement production plants, oil refining facilities,the chlor-alkali industry, vinyl chloride industry, mining operations,and smelting operations. Re-emissions occur when mercury deposited insoils is re-dispersed via floods or forest fires. Mercury absorbed insoil and/or deposited in soil can be released back into the water viarain runoff and/or flooding. As such, soil erosion contributes to thisproblem. Forest fires, whether they are acts of nature, arson, ordeliberate deforestation burning, re-emits mercury back into the airand/or water sources only to be deposited again elsewhere. Naturallyoccurring emissions include volcanoes and geothermal vents. It isestimated that about half of all mercury released into the atmosphere isfrom naturally occurring events such as volcanos and thermal vents.

As noted above, coal burning plants release a large quantity of mercuryand other contaminants into the environment each year. Accordingly,there are many ongoing efforts to reduce the amount of hazardouscontaminants in the flue gas emissions produced by coal burning plants.Many coal burning plants in the USA are equipped with emissions controlsystems which capture, contain, and/or recover hazardous elements suchas mercury. In coal burning plants, coal is burned to boil water,turning the water into steam, which is used to run electric generators.The flue gas emissions from the burning of coal are often conveyedthrough a conduit system to a fluid gas desulfurization unit and/or aspray dryer system, which remove some emissions and some of the noxiousfumes such as sulfur dioxide (SO₂) and hydrogen chloride (HCl) from theflue gases. A typical conduit system then routes the flow of flue gasesto a wet or dry scrubber where more sulfur dioxide, hydrogen chloride,and fly ash are removed. The flow of flue gases is routed through a baghouse where particulates are separated from the airflow in the fluegases, similar to the way a household vacuum cleaner bag works. The fluegases pass through the filter-like bags, which have a porosity allowingairflow but not the larger particulates traveling in the airflow. Thesurfaces of the filter bags are shaken and/or cleaned to collect thecaptured particulates so that they can be disposed of. Usually, thesedeposits are hazardous emissions themselves and must be disposed ofaccordingly. The balance of flue gasses that make it through this typeof emissions control system is then allowed to escape through a tallsmoke stack and released into the atmosphere.

The problem with this type of emissions control system is that it isvirtually ineffective to capture and/or collect the heavy metals such asmercury contained in a metallic vapor and metallic compound vapor form.Since the coal fired burning systems burn coal at relatively elevatedtemperatures near 1,500 degrees Fahrenheit, the mercury is convertedinto nano-sized vapor particles that are able to slip through even themost capable filter systems. As a result, significant emissions of airborne mercury and other hazardous contaminants are released into theatmosphere.

In an effort to capture and collect mercury from coal fired systemsand/or other emission sources of mercury, several known systems havebeen developed to address the problem, which generally fall into one ofthree categories.

The first category is a group of methods and/or systems that capturemercury by injecting a sorbent into the flue gas stream. Other than anoble metal, the most common sorbent material used is activated carbonand/or biochar. Activated carbon is often halogenated with bromine.Biochar is a form of charcoal and is rich in carbon. The injection ofsorbents into the flue gas helps to capture contaminants in one and/orany combination of the following typical emissions control devices: anelectrostatic precipitator, a fluidized gas desulfurization system,scrubber systems, or fabric filter systems. There are several variationsof these systems, requiring the injection of activated carbon at variouspoints of the emission control system after combustion of the coal. Someexemplary methods and/or systems of the first category are disclosed inU.S. Pat. Nos. 7,578,869, 7,575,629, 7,494,632, 7,306,774, 7,850,764,7,704,920, 7,141,091, 6,905,534, 6,712,878, 6,695,894, 6,558,454,6,451,094, 6,136,072, 7,618,603, 7,494,632, 8,747,676, 8,241,398,8,728,974, 8,728,217, 8,721,777, 8,685,351, and 8,029,600.

The second category is a group of methods and/or systems that pretreatthe coal fuel before combustion in an effort to reduce the levels ofmercury in the coal fuel. Some exemplary methods and/or systems of thesecond category are described in U.S. Pat. Nos. 7,540,384, 7,275,644,8,651,282, 8,523,963, 8,579,999, 8,062,410, and 7,987,613. All of themethods and/or systems set forth in these exemplary patents generatelarge volumes of unusable coal, which is also considered a hazardouswaste. As a result, the methods and/or systems of the second category ofknown solutions are inefficient and expensive to operate. Furthermore,substantial capital and physical space is often required for thepretreatment of coal, making it impractical to retrofit many existingemission control systems with the necessary equipment.

The third category is a group of methods and/or systems that inject acatalyst into the emissions control equipment upstream of the activatedcarbon injection system. The catalyst in these methods and/or systemsionize the mercury making it easier to collect and remove the mercuryfrom the flue gasses. However, the efficiency of such methods and/orsystems is poor and operating costs are high, such that the methodsand/or systems of the third category of known solutions are not costeffective. Examples of the third category of are described in U.S. Pat.Nos. 8,480,791, 8,241,398, 7,753,992, and 7,731,781. In addition tothese examples, U.S. Pat. No. 7,214,254 discloses a method and apparatusfor regenerating expensive sorbent materials by using a microwave and afluid bed reactor. The method selectively vaporizes mercury from thesorbent, at which point the mercury can be caught in a specializedfilter or condensed and collected. The use of microwave generationrenders this method impractical for large scale commercial applicationsand is therefore only useful for the regeneration of expensive sorbents.Another example is found in U.S. Patent Application Publication No.2006/0120935, which discloses a method for the removal of mercury fromflue gasses using any one of several substrate materials to formchemical attractions to the mercury as the flue gasses pass through theemissions control equipment. This method is also impractical for largescale commercial use. Therefore, current emissions control systems andmethods generally operate by transferring the hazardous contaminantsfrom a gaseous emission to a non-gaseous emission, which creates anotherset of emission control problems.

While many laws and regulations focus on metallic vapor emissions, otherforms of emissions containing hazardous contaminants such as slurryand/or slurry-like emissions, sludge and/or sludge-like emissions,liquid and/or liquid-like emissions, and other emission variationsshould not be overlooked. All of the emission types listed may alsorequire processing where the hazardous contaminants they contain can beneutralized, captured, collected, removed, disposed of, and/or properlycontained by one means or another. Historically, the most cost effectiveand most widely used process for removing hazardous contaminantsutilizes activated carbon (in one form or another), through which theemissions pass. Accordingly, the demand for activated carbon in the USAis expected to grow each year through 2017 with over one billion poundsrequired each and every year at a cost to industries of over$1-$1.50/pound. This equates to about $1 billion annually. Most of theprojected increase in demand for activated carbon is driven by theimplementation of EPA promulgated regulations, which require utilitiesand industrial manufacturers to upgrade coal-fired power plants tocomply with ever more stringent requirements.

In addition to the ever more stringent gaseous emissions regulations,the EPA has implemented tougher regulations for non-gaseous emissionsthrough The Clean Water Act, which must be fully complied with by 2016.The combination of increasing regulations on all types of emissionsimpacts multiple types of emissions that are produced by a variety ofdifferent industries. Some industries, such as electrical powerproducers, who burn fuel to generate power, produce primary gaseousemissions containing hazardous contaminants. Per industry standards,these gaseous emissions are exposed to activated carbon materials in aneffort to capture enough volume of hazardous contaminants so as torender the gaseous emission at or below allowable limits forcontaminants. The process of removing the hazardous contaminants fromthe gaseous emissions generated from burning these fuels results inand/or generates secondary non-gaseous emissions in the form ofliquid-like or slurry-like substances containing the hazardouscontaminants. The hazardous contaminants in the second non-gaseousemissions must also be captured and/or contained appropriately toprevent the hazardous contaminants from being discharged into theenvironment. Both the primary gaseous emissions and the secondarynon-gaseous emissions require a means of properly capturing and/orreclaiming and/or confining enough of the hazardous contaminants tocomply with environmental regulations. The industrial costs associatedwith known available processes capable of accomplishing the removal ofthe hazardous contaminants from the secondary non-gaseous emissions arealmost so cost prohibitive that some industries are forced to shut downfacilities if they cannot pass the costs along to consumers.

In accordance with some practices, non-gaseous emissions, which areconsidered to be hazardous because they contain elevated levels ofcontaminants, are consigned and contained for long-term storage inponds, piles, or drying beds. While such practices isolate the hazardouscontaminants, they are expensive and consume land area withoutneutralizing the hazardous contaminants themselves, which can result inenvironmental hazards at the containment sites. One example of anon-gaseous emission is fly ash, which is a naturally-occurring productfrom the combustion of coal. Fly ash is basically identical incomposition to volcanic ash. Fly ash contains trace concentrations (i.e.amounts) of many heavy metals and other known hazardous and toxiccontaminants including mercury, beryllium, cadmium, barium, chromium,copper, lead, molybdenum, nickel, radium, selenium, thorium, uranium,vanadium, and zinc. Some estimates suggest that as much as 10% of thecoal burned in the USA consists of unburnable material, which becomesash. As a result, the concentrations of hazardous trace elements in coalash are as much as 10 times higher than the concentration of suchelements in the original coal.

Fly ash is considered to be a pozzolan material with a long history ofbeing used in the production of concrete because when it is mixed withcalcium hydroxide a cementitious material is formed that aggregates withwater and other compounds to produce a concrete mix well suited forroads, airport runways, and bridges. The fly ash produced in coalburning plants is flue-ash that is comprised of very fine particleswhich rise with the flue gases. Ash that does not rise is often calledbottom ash. In the early days of coal burning plants, fly ash was simplyreleased into the atmosphere. In recent decades, environmentalregulations have required emission controls to be installed to preventthe release of fly ash into the atmosphere. In many plants the use ofelectrostatic precipitators capture the fly ash before it can reach thechimneys and exit to atmosphere. Typically the bottom ash is mixed withthe captured fly ash to form what is known as coal ash. Usually, the flyash contains higher levels of hazardous contaminants than the bottomash, which is why mixing bottom ash with fly ash brings the proportionallevels of hazardous contaminants within compliance of most standards fornon-gaseous emissions. However, future standards may reclassify fly ashas a hazardous material. If fly ash is reclassified as a hazardousmaterial it will be prevented from being utilized in the production ofcement, asphalt, and many other widely used applications. It has beenestimated by some studies that the cost increase of concrete in the USAalone would exceed $5 billion per year as a result of a ban on the usageof fly ash in concrete production. The increase in cost is a directresult of more expensive alternative materials being used in place offly ash. In addition, no other known material is suitable as a directreplacement for fly ash in cement due to its unique physical properties.

Reports indicate that in the USA over 130 million tons of fly ash isproduced annually by over 450 coal-fired power plants. Some reportsestimate that barely 40% of this fly ash is re-used, indicating that asmuch as 52 million annual tons of fly ash is reused leaving as much as78 million annual tons stored in bulk in slurry ponds and piles. Fly ashis typically stored in wet slurry ponds to minimize the potential offugitive particulates becoming airborne, which could convey contaminantsout of bulk storage and into the atmosphere and surrounding environment.In addition to airborne releases of bulk storage fly ash, there is athreat of breach and/or failure of the containment systems required forthe long term containment of fly ash. One famous example of a breachoccurred in 2008 in Tennessee, where an embankment of a wet storage flyash pond collapsed, spilling 5.4 million cubic yards of fly ash. Thespill damaged several homes and contaminated a nearby river. Cleanupcosts are still ongoing at the time of this application and could exceed$1.2 billion.

In another example, non-gaseous emissions may be found as byproducts intypical wastewater generation systems of coal burning facilities. Intypical wastewater generation systems, large volumes of water come fromboiler blow down and cooling water processes. These large volumes ofwastewater contain relatively low levels of contaminants and are used todilute other waste streams containing much higher levels ofcontamination. The contaminated wastewater streams typically dischargedfrom scrubber systems is diluted with the large volumes of wastewaterfrom the boiler blow down and/or cooling water processes and thentreated in large continuous mix tanks with lime to form gypsum, which isthen pumped into settling ponds. During this process certain amounts ofmercury and other heavy metals are entrained with the gypsum andstabilized for use in wallboard and cement. This gypsum is generallyconsidered to be non-leaching and is not considered a pollution hazard.However, the water from the settling ponds is generally discharged intothe waterways. Current regulations allow this ongoing discharge, butlooming regulations propose that certain contaminants and/or levels ofthose contaminants be mandated as a hazardous pollution.

With regard to removing mercury and heavy metals from non-gaseousindustrial wastewater streams, the use of carbonate, phosphate, orsulfur is often employed in an effort to reduce hazardous contaminantsto low residual levels. One known method for removing mercury and otherhazardous contaminants from industrial wastewater streams is chemicalprecipitation reaction. Another known method utilizes ion exchange. Oneof the primary problems with the chemical precipitation reaction and ionexchange methods is that these methods are not sufficient to fullycomply with the ever more stringent EPA regulations for non-gaseousemissions when the amount of contaminants is high, such as for treatingfly ash slurry emissions.

Another source of contaminated non-gaseous emissions is from maritimevessels waste discharge and/or ballast discharge. Commercial ships suchas cargo ships and tankers have both waste and ballast discharge.Entertainment cruise liners also have discharge effluents to deal withat port stops. Additionally, military and defense vessels havesignificant discharge effluents.

Another significant discharge effluent is generated by offshore drillingoperations. Treatment of effluent waste on-site at the offshore rig ismuch less expensive than transportation of waste to land for treatment.Therefore, efficient filtering of offshore waste prior to discharge intothe sea is necessary to maintain appropriate and acceptable ecologyrequirements. Virtually all contaminated emissions applications vary inthe types and/or specific concentrations of contaminates in theemissions. Therefore, a one-size-fits-all approach for a suitablesorbent which is optimized for all possible contaminated emissionsapplications is not possible. There is a need for providing applicationspecific sorbent solutions for optimizing effective emissions controlbased on specific contaminates resident in emissions. A further needexists to be able to adjust the sorbent application during use tocorrespond to changing levels and/or types of contaminates resident inthe emissions.

There are also various known commercial emissions control methods andsystems sold under different tradenames for treating secondarynon-gaseous emissions. One treatment method known by the tradename BluePRO is a reactive filtration process that removes mercury from secondarynon-gaseous emissions using co-precipitation and absorption. Anothertreatment method known by the tradename MERSORB-LW uses a granular coalbased absorbent to remove mercury from secondary non-gaseous emissionsby co-precipitation and absorption. Another treatment method known asChloralkali Electrolysis Wastewater removes mercury from secondarynon-gaseous emissions during the electrolytic production of chlorine.Another treatment method uses absorption kinetics and activated carbonderived from fertilizer waste to remove mercury from secondarynon-gaseous emissions. Another treatment method uses a porous cellulosecarrier modified with polyethyleneimine as an absorbent to removemercury from secondary non-gaseous emissions. Another treatment methoduses microorganisms in an enzymatic reduction to remove mercury fromsecondary non-gaseous emissions. Yet another treatment method known bythe tradename MerCUR_(x)E uses chemical precipitation reactions to treatcontaminated liquid-like non-gaseous emissions.

A common treatment method by some of the emissions control systems is todilute contaminates instead of removing them from the emissions. As aresult, if the PPM levels of a contaminate in an emission exceeds theallowable levels, then rather than removing the contaminate to reducethe level, additional non-contaminated volume is added to the emissionso that the resulting PPM levels are reduced to allowable levels, eventhough the actual amount of contaminate being allowed remains unchanged.There is a serious need to overcome this practice of dilution byproviding an effective emissions control method which not only reducesthe PPM level of contaminates, but removes the contaminates from theemissions.

SUMMARY OF THE INVENTION

In various embodiments, the present invention provides a method ofextracting a target material from a medium. The method includescontacting a copper zinc tin sulfur (CZTS) sorbent with the targetmaterial in the medium including the target material to form a used CZTSsorbent that includes the target material. The method also includesseparating the used CZTS sorbent from the medium.

In various embodiments, the present invention provides a method ofextracting a target material from a medium. The method includescontacting a copper zinc tin sulfur (CZTS) sorbent with the targetmaterial in the medium including the target material to form a used CZTSsorbent that includes the target material, wherein the target materialincludes mercury, a precious metal, a rare earth metal, or a combinationthereof. The method includes separating the used CZTS sorbent from themedium. The method includes removing the target material from the usedCZTS sorbent, to obtain an extract including the target material.

In various embodiments, the present invention provides a method ofextracting a target material from a medium. The method includescontacting a copper zinc tin sulfur (CZTS) sorbent with the targetmaterial in the medium including the target material to form a used CZTSsorbent that includes the target material, wherein the target materialincludes a precious metal, a rare earth metal, or a combination thereof,wherein the medium includes a liquid used in or obtained from a miningoperation. The method includes separating the used CZTS sorbent from themedium. The method also includes removing the target material from theused CZTS sorbent, to obtain an extract including the target material.

In various embodiments, the present invention provides a method ofextracting a target material from a medium. The method includescontacting a copper zinc tin sulfur (CZTS) sorbent with the targetmaterial in the medium including the target material to form a used CZTSsorbent that includes the target material, wherein the target materialincludes a polluting substance, a toxic substance, a poisonoussubstance, or a combination thereof, wherein the medium includes fluegas from a coal-fired electrical plant, water from the coal-firedelectrical plant, or a combination thereof. The method includesseparating the used CZTS sorbent from the medium. The method alsoincludes removing the target material from the used CZTS sorbent, toobtain an extract including the target material.

In various embodiments, the present invention provides a method offorming a CZTS sorbent. The method includes combining copper, a compoundthereof, or a salt thereof; zinc, a compound thereof, or a salt thereof;tin, a compound thereof, or a salt thereof; and sulfur, a compoundthereof, or a salt thereof; to form a starting material mixture. Themethod also includes processing the starting material mixture underconditions suitable to form the CZTS sorbent.

BRIEF DESCRIPTION OF THE FIGURES

The drawings illustrate generally, by way of example, but not by way oflimitation, various embodiments of the present invention.

FIG. 1 is a schematic diagram illustrating a known layout for a coalburning power plant;

FIG. 2 is a schematic diagram illustrating a known layout for anemissions control system used to remove contaminants from emissionsproduced by coal burning power plants of the type shown in FIG. 1;

FIG. 3 is a schematic diagram of the emissions control system shown inFIG. 2 where the emissions control system has been modified by theadding an exemplary reverse venturi apparatus that is constructed inaccordance with the subject disclosure;

FIG. 4A is a side cross-sectional view of an exemplary reverse venturiapparatus constructed in accordance with the subject disclosure, whichincludes a housing having an entry portion, an enlarged portion, and anexit portion;

FIG. 4B is a front cross-sectional view of the entry portion of thehousing of the exemplary reverse venturi apparatus illustrated in FIG.4A;

FIG. 4C is a front cross-sectional view of the enlarged portion of thehousing of the exemplary reverse venturi apparatus illustrated in FIG.4A;

FIG. 4D is a front cross-sectional view of the exit portion of thehousing of the exemplary reverse venturi apparatus illustrated in FIG.4A;

FIG. 5 is a side cross-sectional view of another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurewhere a series of staggered baffles are disposed in the enlarged portionof the housing creating a serpentine shaped flow path for the emissions;

FIG. 6A is a side cross-sectional view of another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurewhere an auger-shaped baffle is disposed in the enlarged portion of thehousing creating a helically shaped flow path for the emissions;

FIG. 6B is a front perspective view of the auger-shaped baffleillustrated in the exemplary reverse venturi apparatus shown in FIG. 6A;

FIG. 7A is a side cross-sectional view of another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurewhere a plurality of spaced apart baffles are disposed in the enlargedportion of the housing;

FIG. 7B is a front cross-sectional view of the exemplary reverse venturiapparatus illustrated in FIG. 7A taken along section line A-A whereorifices in one of the baffles are shown;

FIG. 8 is a side cross-sectional view of another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurewhere a plurality of fragments are disposed in the enlarged portion ofthe housing;

FIG. 9 is a side cross-sectional view of another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurewhere a plurality of entangled strands are disposed in the enlargedportion of the housing forming a wool-like material therein;

FIG. 10 is a side cross-sectional view of another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurewhere a filter element is disposed in the enlarged portion of thehousing;

FIG. 11 is a side cross-sectional view of another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurewhere the enlarged portion of the housing contains a plurality ofbaffles and a plurality of fragments of varying sizes that are disposedin between adjacent baffles;

FIG. 12A is a front elevation view showing one exemplary size of thefragments contained in the enlarged portion of the housing of theexemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 12B is a front elevation view showing another exemplary size of thefragments contained in the enlarged portion of the housing of theexemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 12C is a front elevation view showing another exemplary size of thefragments contained in the enlarged portion of the housing of theexemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 12D is a front elevation view showing another exemplary size of thefragments contained in the enlarged portion of the housing of theexemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 13A is a front elevation view showing one exemplary piece of loosematerial with an asterisk-like shape that in combination with otherpieces may be used to replace the fragments shown in the exemplaryreverse venturi apparatus illustrated in FIGS. 8 and 11;

FIG. 13B is a front elevation view showing one exemplary crystallineflake that in combination with other crystalline flakes may be used toreplace the fragments shown in the exemplary reverse venturi apparatusillustrated in FIGS. 8 and 11;

FIG. 13C is a front elevation view showing one exemplary wire coil thatin combination with other wire coils may be used to replace thefragments shown in the exemplary reverse venturi apparatus illustratedin FIGS. 8 and 11;

FIG. 14 is a side cross-sectional view showing another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurethat includes two separate enlarged portions that are joined together inseries;

FIG. 15 is a side cross-sectional view showing another exemplary reverseventuri apparatus constructed in accordance with the subject disclosurethat includes two separate enlarged portions that are joined together inparallel;

FIG. 16 is a side cross-sectional view showing another exemplary reverseventuri apparatus constructed in accordance with the subject disclosure;

FIG. 17 is a block flow diagram illustrating a known method for removingcontaminants from gaseous emissions;

FIG. 18A is a block diagram illustrating the method for removingcontaminants from gaseous emissions illustrated in FIG. 17 where themethod has been modified by adding steps for injecting a sorbent intothe gaseous emissions at a first introduction point and subsequentlypassing the gaseous emissions through a reverse venturi apparatus;

FIG. 18B is a block diagram illustrating the method for removingcontaminants from gaseous emissions illustrated in FIG. 17 where themethod has been modified by adding steps for injecting the sorbent intothe gaseous emissions at a second introduction point and subsequentlypassing the gaseous emissions through the reverse venturi apparatus;

FIG. 19 is a block diagram illustrating a known method for removingcontaminants from non-gaseous emissions that calls for depositing thenon-gaseous emissions in a settling pond;

FIG. 20 is a block diagram illustrating the method for removingcontaminants from non-gaseous emissions illustrated in FIG. 19 where themethod has been modified by adding steps for treating a portion of thenon-gaseous emissions extracted from the settling pond with a sorbent;

FIG. 21 is a graph illustrating the percentage of contaminants removedfrom emissions by known emissions control systems and the percentage ofcontaminants removed from emissions by the apparatus and methodsdisclosed herein;

FIG. 22 is block flow diagram illustrating an exemplary method of usinga reverse venturi shaped fluidized bed apparatus to remove contaminatesfrom gaseous emissions and clean the reactive material that separatesthe contaminates from the gaseous emissions;

FIG. 23 is block flow diagram illustrating an exemplary method of usinga reverse venturi shaped fluidized bed apparatus to remove contaminatesfrom non-gaseous emissions and clean the reactive material thatseparates the contaminates from the non-gaseous emissions;

FIG. 24 is a flow diagram illustrating extended non-turbulent emissionsflow through an exemplary reverse venturi shaped fluidized bed apparatusand exemplary method steps for cleaning and recycling the sorbent thatseparates the contaminates from the emissions;

FIG. 25 is block flow diagram illustrating an exemplary method using areverse venturi shaped fluidized bed apparatus with a tilting mechanismmounted to a transportable platform deck where the housing of thereverse venturi shaped fluidized bed apparatus is oriented relativelyparallel to the platform deck in order to remove contaminates fromgaseous emissions;

FIG. 26 is block flow diagram illustrating an exemplary method using areverse venturi shaped fluidized bed apparatus with a tilting mechanismmounted to a transportable platform deck where the housing of thereverse venturi shaped fluidized bed apparatus is oriented relativelytransverse to the platform deck in order to remove contaminates fromnon-gaseous emissions;

FIG. 27 is a matrix showing specific types of contaminates matchedagainst the effectiveness of the disclosed CZTS Alloy sorbents comparedto activated carbon and zeolite sorbents for gaseous and non-gaseousemissions;

FIG. 28 is a schematic diagram showing specific CZTS Alloy sorbentscompared to other specific types of sorbents for gaseous and non-gaseousemissions;

FIG. 29 is a matrix showing prior art sorbents and their ability toseparate from contaminates in gaseous and non-gaseous emissions and bereused;

FIG. 30 is a matrix showing the disclosed broad-spectrum CZTS Alloysorbents and their ability to separate from contaminates in gaseous andnon-gaseous emissions and be reused;

FIG. 31 is a block diagram showing a method routing contaminated gaseousemissions through different filters containing specific effectivesorbents that match the types and/or levels of contaminates resident inthe gaseous emissions;

FIG. 32 is a block diagram showing a method routing contaminatednon-gaseous emissions through different filters containing specificeffective sorbents that match the types and/or levels of contaminatesresident in the non-gaseous emissions; and

FIG. 33 is a flow diagram illustrating extended non-turbulent emissionsflow through an exemplary reverse venturi shaped fluidized bed apparatusand exemplary method steps for cleaning and recycling the sorbent thatseparates the contaminants from the emissions by using a series ofsorbent recycling subsystems for CZTS sorbents, CZTS-Alloy sorbents,and/or CZTS-Mixture sorbents.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Throughout this document, values expressed in a range format should beinterpreted in a flexible manner to include not only the numericalvalues explicitly recited as the limits of the range, but also toinclude all the individual numerical values or sub-ranges encompassedwithin that range as if each numerical value and sub-range is explicitlyrecited. For example, a range of “about 0.1% to about 5%” or “about 0.1%to 5%” should be interpreted to include not just about 0.1% to about 5%,but also the individual values (e.g., 1%, 2%, 3%, and 4%) and thesub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within theindicated range. The statement “about X to Y” has the same meaning as“about X to about Y,” unless indicated otherwise. Likewise, thestatement “about X, Y, or about Z” has the same meaning as “about X,about Y, or about Z,” unless indicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.The statement “at least one of A and B” or “at least one of A or B” hasthe same meaning as “A, B, or A and B.” In addition, it is to beunderstood that the phraseology or terminology employed herein, and nototherwise defined, is for the purpose of description only and not oflimitation. Any use of section headings is intended to aid reading ofthe document and is not to be interpreted as limiting; information thatis relevant to a section heading may occur within or outside of thatparticular section.

In the methods described herein, the acts can be carried out in anyorder without departing from the principles of the invention, exceptwhen a temporal or operational sequence is explicitly recited.Furthermore, specified acts can be carried out concurrently unlessexplicit claim language recites that they be carried out separately. Forexample, a claimed act of doing X and a claimed act of doing Y can beconducted simultaneously within a single operation, and the resultingprocess will fall within the literal scope of the claimed process.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range, and includes the exactstated value or range.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or100%. The term “substantially free of” as used herein can mean havingnone or having a trivial amount of, such that the amount of materialpresent does not affect the material properties of the compositionincluding the material, such that about 0 wt % to about 5 wt % of thecomposition is the material, or about 0 wt % to about 1 wt %, or about 5wt % or less, or less than, equal to, or greater than about 4.5 wt %, 4,3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1,0.01, or about 0.001 wt % or less, or about 0 wt %.

Referring to the Figures, wherein like numerals indicate correspondingparts throughout the several views, an apparatus and methods forremoving contaminants from industrial emissions are illustrated.

Example embodiments will now be described more fully with reference tothe accompanying drawings. Example embodiments are provided so that thisdisclosure will be thorough, and will fully convey the scope to thosewho are skilled in the art. Numerous specific details are set forth suchas examples of specific components, devices, and methods, to provide athorough understanding of embodiments of the present disclosure. It willbe apparent to those skilled in the art that specific details need notbe employed, that example embodiments may be embodied in many differentforms and that neither should be construed to limit the scope of thedisclosure. In some example embodiments, well-known processes,well-known device structures, and well-known technologies are notdescribed in detail.

The terminology used herein is for the purpose of describing particularexample embodiments only and is not intended to be limiting. As usedherein, the singular forms “a,” “an,” and “the” may be intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. The terms “comprises,” “comprising,” “including,” and“having,” are inclusive and therefore specify the presence of statedfeatures, integers, steps, operations, elements, and/or components, butdo not preclude the presence or addition of one or more other features,integers, steps, operations, elements, components, and/or groupsthereof. The method steps, processes, and operations described hereinare not to be construed as necessarily requiring their performance inthe particular order discussed or illustrated, unless specificallyidentified as an order of performance. It is also to be understood thatadditional or alternative steps may be employed.

When an element or layer is referred to as being “on,” “engaged to,”“connected to,” or “coupled to” another element or layer, it may bedirectly on, engaged, connected or coupled to the other element orlayer, or intervening elements or layers may be present. In contrast,when an element is referred to as being “directly on,” “directly engagedto,” “directly connected to,” or “directly coupled to” another elementor layer, there may be no intervening elements or layers present. Otherwords used to describe the relationship between elements should beinterpreted in a like fashion (e.g., “between” versus “directlybetween,” “adjacent” versus “directly adjacent,” etc.). As used herein,the term “and/or” includes any and all combinations of one or more ofthe associated listed items.

Although the terms first, second, third, etc. may be used herein todescribe various elements, components, regions, layers and/or sections,these elements, components, regions, layers and/or sections should notbe limited by these terms. These terms may be only used to distinguishone element, component, region, layer or section from another region,layer or section. Terms such as “first,” “second,” and other numericalterms when used herein do not imply a sequence or order unless clearlyindicated by the context. Thus, a first element, component, region,layer or section discussed below could be termed a second element,component, region, layer or section without departing from the teachingsof the example embodiments.

Spatially relative terms, such as “inner,” “outer,” “beneath,” “below,”“lower,” “above,” “upper,” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. Spatiallyrelative terms may be intended to encompass different orientations ofthe device in use or operation in addition to the orientation depictedin the figures. For example, if the device in the figures is turnedover, elements described as “below” or “beneath” other elements orfeatures would then be oriented “above” the other elements or features.Thus, the example term “below” can encompass both an orientation ofabove and below. The device may be otherwise oriented (rotated 90degrees or at other orientations) and the spatially relative descriptorsused herein interpreted accordingly.

The term “conduit”, as used herein, is intended to cover all referencesto pipe as may be normally used in conveying liquid, and/or liquid-likeemissions and gaseous and/or gaseous-like emissions. No preference isgiven or implied concerning the actual method of conveyance of emissionsregardless of the type of emissions. The term “ambient temperature” asused herein refers to the temperature of the surrounding environment(e.g., standard temperature and pressure “STP”). Additionally, it shouldbe understood that the terms “contaminate(s)” and “contaminant(s)” areused interchangeably in the present disclosure.

In accordance with one aspect of the subject disclosure, an apparatusfor removing contaminants from emissions is disclosed. The apparatusincludes a housing that is shaped as a reverse venturi. The housingincludes an entry portion for receiving the emissions at apre-determined entry flow rate, an exit portion for expelling theemissions at a pre-determined exit flow rate, and an enlarged portiondisposed between the entry portion and the exit portion of the housingfor trapping the contaminants in the emissions. The entry portion, theexit portion, and the enlarged portion of the housing are arranged influid communication with each other. In addition, the entry portion ofthe housing has an entry portion cross-sectional area, the exit portionof said housing has an exit portion cross-sectional area, and theenlarged portion of the housing has an enlarged portion cross-sectionalarea. In accordance with the reverse venturi shape of the housing, theenlarged portion cross-sectional area is larger than the entry portioncross-sectional area and the exit portion cross-sectional area. Due tothis geometry of the housing, the emissions entering the enlargedportion of the housing slow down and pass through the enlarged portionof the housing at a slower velocity relative to a velocity of theemissions passing through the entry portion and the exit portion of thehousing. Because the flow of the emissions slows down in the enlargedportion of the housing, a dwell time of the emissions in the enlargedportion of the housing is increased.

The apparatus also includes a mass of reactive material including one ormore sorbents that are disposed within the enlarged portion of thehousing. The mass of reactive material has a reactive outer surface thatis disposed in contact with the emissions. Furthermore, the mass ofreactive material contains an amalgam forming metal at the reactiveouter surface. The amalgam forming metal in the mass of reactivematerial chemically binds at least some of the contaminants in theemissions that are passing through the enlarged portion of the housingto the reactive outer surface of the mass of reactive material. One ormore sorbent recycling subsystems are disposed in fluid communicationwith the housing. Each sorbent recycling subsystem receives sorbent fromthe housing via a sorbent discharge port and returns clean sorbent tothe housing via a sorbent return port. The sorbent recyclingsubsystem(s) include a chemical reagent for separating contaminants fromthe sorbent in a cleaning and rejuvenation process before the cleanedsorbent is returned to the housing of the fluidized bed apparatus.

In accordance with another aspect of the subject disclosure, anemissions control method is disclosed for removing contaminants fromemissions. The method includes the steps of: routing the emissions intoa treatment system including a reverse venturi shaped fluidized bedapparatus containing one or more sorbents that chemically binds withcontaminants carried in the emissions, and routing the emissions awayfrom the reverse venturi shaped fluidized bed apparatus. In accordancewith this method, the sorbent(s) is/are selected from a group ofmaterials including: copper, zinc, tin, sulfur (CZTS) sorbents, copper,zinc, tin, sulfur (CZTS) alloy sorbents, and copper, zinc, tin, sulfur(CZTS) mixture sorbents. The method further includes the step of routingthe sorbent(s) through one or more sorbent recycling subsystems forchemical cleaning and rejuvenation.

It is important to maintain optimum process conditions of the sorbentsbeing used to remove contaminated emissions from the reverse venturishaped fluidized bed apparatus. Therefore, the sorbent is routed fromthe reverse venturi shaped fluidized bed apparatus and into a sorbentrecycling subsystem. The sorbent recycling subsystem is designed toclean and/or rejuvenate the sorbent to optimum conditions beforereturning the sorbent back into the reverse venturi shaped fluidized bedapparatus. The sorbent recycling subsystem is also designed to separate,and route for disposal, spent and exhausted sorbent from the rest of thesorbent that can be cleaned and/or rejuvenated. The sorbent recyclingsubsystem is further designed to separate captured contaminates from thesorbent for recycled use in various industries or for proper disposal ifthere is not a viable recycling option. The sorbent recycling subsystemis further designed to supplement and/or replace sorbent that has beenseparated for disposal and/or sorbent that has been consumed during thenormal operation of removing contaminants from contaminated emissions.

In accordance with another aspect of the subject disclosure, the sorbentrecycling subsystem includes one or more monitoring sensors that providecontinuous in-line testing and monitoring feedback to maintain constantand consistent optimum sorbent conditions. One exemplary embodiment ofthe subject disclosure provides at least three separate locations inwhich three separate sorbent recycling subsystems are installed andconfigured. A first sorbent recycling subsystem location is provided forCZTS sorbents. A second sorbent recycling subsystem location is providedfor CZTS-Alloy sorbents. A third sorbent recycling subsystem location isprovided for CZTS-Mixture sorbents. Specific emissions requirements maydictate which sorbent recycling subsystem is specifically required.Depending on the levels of contamination in the reverse venturifluidized bed apparatus, the reverse venturi fluidized bed apparatus canbe configured to use all three of the sorbent recycling subsystems, usenone of the sorbent recycling subsystems, or multiple installations ofthe same sorbent recycling subsystem may be arranged at multiplelocations along the reverse venturi fluidized bed apparatus and usedsimultaneously.

In addition to the advantage of significant savings, the subjectapparatus and method are more effective at removing hazardouscontaminants from gaseous and non-gaseous emissions compared to knownemissions control systems and methods. It is estimated that theseimprovements are significant enough to enable industries to meet and/orexceed the projected regulation requirements, which is not economicallyviable with current technology. Therefore, the subject apparatus andmethods have the potential of allowing the continued use of fly ash,even if regulatory requirements reclassify fly ash as a hazardousmaterial, thus avoiding significant increased cost to the constructionindustry, utility power generation industry, and other industriesproducing non-gaseous ash-type byproducts.

The reverse venturi shaped fluidized bed apparatus may be specificallysized with a certain length to diameter ratio to provide optimumrestrictive residence time of the emissions as they pass through thespecialized sorbent housed in the device. Through testing and trials, ithas been determined that an optimum length to diameter ratio for thehousing of the fluidized bed apparatus is between 2.9:1 and 9.8:1 withan exemplary preference of 4.4:1. Therefore, in one exemplary preferredembodiment the diameter is 4.5 feet with a length of 19.8 feet inlength, which gives a length to diameter ratio of 4.4:1.

Another feature of the exemplary reverse venturi shaped fluidized beddevice is to have predominately rounded outwardly projecting convex endswhen viewed from either end outside the vessel. Testing of exemplaryexamples of the system with a fluidized bed apparatus constructed inthis fashion have demonstrated that residence time (the time in whichthe emissions are in contact with the sorbent) is maximized because theflow of the emissions is randomly turned back on itself with minimizedcavitation turbulence, therefore increasing maximized intimate contact.The predominately rounded outwardly projecting convex ends provide arelatively smooth return flow at both ends of the fluidized bedapparatus with minimal cavitation turbulence of the emissions. Turbulentflow with cavitation through a filter is known to impede and/or disruptflow. Extended residence time in and through the fluidized bed apparatusis desired for optimized contaminate capture and removal from theemissions; however, extended residence time is not optimized if the flowis turbulent flow with cavitation. Various baffles and/or otherapplication specific flow restriction obstacles can be incorporated intothe housing of the fluidized bed apparatus.

In accordance with another aspect of the subject disclosure, anexemplary contaminate removal system is provided with reconfigurablesegmental components. Each system component can be isolated, bypassed,incorporated, and/or reconfigured for application specific requirements.

According to another aspect of the subject disclosure, the emissionscontrol system contains a mass of reactive sorbent including a copper,zinc, tin, sulfur (CZTS) sorbent, a CZTS-Alloy, and/or a copper, zinc,tin, sulfur (CZTS) mixture sorbent in the fluidized bed apparatus. Thefluidized bed apparatus also has additional ports to clean and/orreplace sorbent material. The multiple sorbent recycling subsystemsdisclosed herein provide a method of use for CZTS sorbents, CZTS-Alloysorbents, and/or CZTS-Mixture sorbents. The exemplary emissions controlsystem may further include one or more pre-filters and/or post-filtersthat contain a mass of reactive sorbent. The pre-filters andpost-filters may be plumbed in parallel or series with the fluidized bedapparatus, depending upon applications specific requirements.

Emissions contaminates from industrial applications include: Hg(Mercury), As (Arsenic), Ba (Barium), Cd (Cadmium), Cr (Chromium), Cu(Copper), Pb (Lead), Sn (Tin), P (Phosphorous), NO₂ (Nitrogen Dioxide),NO₃ (Nitrate), NH₃ (Ammonia). The long list of contaminates precludesthe ability to have a one-size-fits-all emissions control solution.Furthermore, emissions control solutions which may work for onecontaminate in a gaseous emission might not be effective for the samecontaminate in a non-gaseous emission, and vice versa.

International standards and regulations, Federal standards andregulations, State standards and regulations, as well as local standardsand regulations all set various levels for allowable parts per million(PPM) of each contaminate in gaseous and/or non-gaseous emissions. Manyof these standards and regulations set different allowable levels forcontaminates depending upon whether the contaminate is resident in agaseous emission compared to a non-gaseous emission.

Testing contaminated emissions can be spot checked and/or usingcontinuous in-line monitoring equipment to determine types and levels ofcontaminates resident in the emissions. Based upon the testing results,specific pre-filters and/or post-filters can be selected for routingcontaminated emissions. Each of the pre-filters and/or post-filterscontain a specific mass of reactive sorbent as a broad-spectrum oftreatment options targeting a specific contaminate resident in theemissions.

The types and/or levels of contaminates resident in emissions changesand/or fluctuates during emissions discharge. Frequent monitoring ofcontaminates and/or continuous in-line monitoring provides capability toadjust selections of specific pre-filters and/or post-filters to bestcorrespond with the specific contaminates resident in the emissions atany given time during discharge flow.

The present disclosure provides a broad-spectrum matrix, which matchesspecific types of contaminates resident in gaseous and non-gaseousemissions with a specific reactive sorbent that is effective in thecapture and removal of the corresponding contaminate. The matrix alsomatches the ability for a specific reactive sorbent to be separated fromspecific captured contaminates so that the contaminate can be eitherrecycled or disposed, as well as whether the sorbent can be rejuvenatedand re-used in the emissions control system.

In addition to permanently installed systems for application specificuse, the subject system can be configured as a transportable system.Transportable system examples include, but are not limited to, truckmounted systems, barge mounted systems, trailer mounted systems, andrail-car systems. Transportable system applications are useful forproviding a bypass to site-built systems by providing a temporary bypassfor emissions so that permanent site-built system can be serviced,inspected, and/or repaired. Transportable systems are also useful toprovide excess filter capabilities to permanent site-built installationsduring times when contaminated emissions flow rates exceed the capacityof the permanent site-built system.

There are also a number of advantages attendant to the specializedsorbent described herein in connection with the disclosed apparatus andmethods. Generally, the sorbent improves the capabilities of thedisclosed emissions equipment to better capture, contain, and/or recyclemercury and other hazardous materials with an efficiency not previouslypossible using known emission control systems and methods. Anothersignificant benefit of the sorbent disclosed herein is that the sorbentcan be used to treat both gaseous and non-gaseous emissions, thusovercoming many of the shortcomings of known methods for treatingcontaminated non-gaseous emissions, including the secondary emissionsgenerated from primary emissions control processes that are used totreat gaseous emissions. In addition, the sorbent described hereinprovides improved capabilities to treat gaseous emissions effectivelyenough to prevent the need for the secondary treatment of non-gaseousemissions that are produced as a by-product of the primary gaseousemissions treatment process. The sorbent disclosed herein is alsobeneficial because it is reusable. Through a rejuvenation process, thehazardous contaminants that chemically bind with the amalgam formingmetal in the sorbent can be harvested away (i.e. removed) from thesorbent, thus restoring the capacity of the sorbent to removecontaminants from the gaseous and/or non-gaseous emissions.

Referring to FIG. 1, a schematic diagram of a typical coal burning powerplant 100 is shown. The coal burning power plant 100 includes anindustrial facility fluid bed reactor 1 that burns one or more types ofcoal fuel 2 to produce electrical power 7. The electrical power 7 maythen be distributed through power lines 8 to an electrical grid.Combustion within the fluid bed reactor 1 is driven by air 3, flame 4,and the coal fuel 2. The combustion process is used to heat water andproduce steam 5. The steam is then used for turning a generator 6, whichproduces the electrical power 7. Gaseous emissions 10 from thecombustion process are released into the environment through stack 9.When the coal burning power plant 100 is not equipped with any emissionscontrol systems (FIG. 1), the emissions 10 include many hazardouscontaminants such as fly ash, mercury (Hg), metallic vapors, sulfurdioxide (SO₂), hydrogen chloride (HCl), and other noxious fumes.

Referring to FIG. 2, a schematic of an updated coal burning power plant200 is shown, which includes a typical emissions control system 202. Theemission control system 202 helps to capture and collect some of thehazardous contaminants in the gaseous emissions 10. The emissionscontrol system 202 conveys the gaseous emissions 10 from a fluid bedreactor 1 where combustion occurs into a wet or dry scrubber 11 thatremoves some of the sulfur dioxide and fly ash contaminants from thegaseous emissions 10. Alternatively or in addition to the conveying thegaseous emissions 10 to the wet or dry scrubber 11, the emissionscontrol system 202 may convey the gaseous emissions 10 into a spraydryer 12 where some sulfur dioxide, noxious fumes, and othercontaminants are captured and collected. The emissions may also berouted through a fabric filter unit 13 (i.e. a bag house), which usesfilter bags to remove particulates from the flow of gaseous emissions10. This system collects and removes many contaminants from the gaseousemissions 10 before the gaseous emissions 10 are released into thesurrounding atmosphere (i.e. the environment) through the stack 9. Theproblem with the typical emissions control system 202 illustrated inFIG. 2 is that the nano-sized contaminants, such as mercury, which iscontained in metallic vapor emissions, easily passes through the wet ordry scrubber 11, spray dryer 12, and the fabric filter unit 13 of theemissions control system 202.

With reference to FIG. 3, a schematic of a modified coal burning powerplant 300 is shown, which includes a sorbent injector 14 and a reverseventuri apparatus 15 in addition to the emissions control system 202shown in FIG. 2. The sorbent injector 14 operates to add a sorbent intothe gaseous emissions 10 and may optionally be disposed upstream of thereverse venturi apparatus 15. More particularly, in the example shown inFIG. 3, the sorbent injector is positioned between the spray dryer 12and the fabric filter unit 13. Although alternative locations for thereverse venturi apparatus 15 are possible, in FIG. 3, the reverseventuri apparatus is positioned between the fabric filter unit 13 andthe stack 9. One primary advantage of this location is that an existingfacility would be able to install the reverse venturi apparatus 15 andsimply apply for a “Modification to Existing Permit”, saving both timeand money compared to applying for a new permit for an entirely newemissions control system. In operation, the gaseous emissions 10 arerouted from the fabric filter unit 13 and to the reverse venturiapparatus 15. As will be explained in greater detail below, the reverseventuri apparatus 15 is constructed with internal features that aresuitable for collecting and capturing significant amounts of mercury,heavy metals, nano-sized particles, and other contaminants. Therefore,the resulting gaseous emissions 10 exiting the stack 9 are virtuallystripped clean of all hazardous contaminants.

With reference to FIGS. 4A-D, the reverse venturi apparatus 15 includesa housing 16 that is shaped as a reverse venturi. It should beappreciated that a venturi may generally be described as a conduit thatfirst narrows from a larger cross-section down to a smallercross-section and then expands from the smaller cross-section back to alarger cross-section. Therefore, the term “reverse venturi”, as usedherein, describes the opposite—a conduit that first expands from asmaller cross-section to a larger cross-section and then narrows backdown from the larger cross-section to a smaller cross-section.Specifically, the housing 16 of the disclosed reverse venturi apparatus15 extends along a central axis 17 and has an entry portion 18, anenlarged portion 19, and an exit portion 20. The entry portion 18 of thehousing 16 is sized to receive the gaseous emissions 10 at apre-determined entry flow rate, which is characterized by an entryvelocity V₁ and pressure P₁. The exit portion 20 of the housing 16 issized to expel the gaseous emissions 10 at a pre-determined exit flowrate, which is characterized by an exit V₃ and pressure P₃. The enlargedportion 19 is disposed between the entry portion 18 and the exit portion20 of the housing 16 and defines an enlarged chamber 21 therein fortrapping the contaminants in the gaseous emissions 10. The enlargedportion 19 of the housing 16 has an interior surface 68 that generallyfaces the central axis 17. The entry portion 18, the enlarged portion19, and the exit portion 20 of the housing 16 are arranged sequentiallyalong the central axis 17 such that the entry portion 18, the enlargedportion 19, and the exit portion 20 of the housing 16 are in fluidcommunication with each other. In other words, the entry portion 18, theenlarged portion 19, and the exit portion 20 of the housing 16 cooperateto form a conduit extending along the central axis 17.

The entry portion 18 of the housing 16 has an entry portioncross-sectional area A₁ that is transverse to the central axis 17 andthe exit portion 20 of the housing 16 has an exit portioncross-sectional area A₃ that is transverse to the central axis 17. Theentry portion cross-sectional area A₁ may equal (i.e. may be the sameas) the exit portion cross-sectional area A₃ such that thepre-determined entry flow rate equals (i.e. is the same as) thepre-determined exit portion flow rate. Alternatively, the entry portioncross-sectional area A₁ may be different (i.e. may be larger or smaller)than the exit portion cross-section area A₃ such that the pre-determinedentry flow rate is different (i.e. is less than or is greater than) thepre-determined exit flow rate. It should be appreciated that the term“flow rate”, as used herein, refers to a volumetric flow rate of theemissions.

The enlarged portion 19 of the housing 16 has an enlarged portioncross-sectional area A₂ that is transverse to the central axis 17 andthat is larger than the entry portion cross-sectional area A_(t) and theexit portion cross-sectional area A₃. Accordingly, the enlarged portion19 is sized such that a flow velocity V₂ of the gaseous emissions 10within the enlarged portion 19 of the housing 16 is less than the flowvelocity V₁ of the gaseous emissions 10 in the entry portion 18 of thehousing 16 and is less than the flow velocity V₃ of the gaseousemissions 10 in the exit portion 20 of the housing 16. This decreasedflow velocity in turn increases a dwell time of the gaseous emissions 10within the enlarged portion 19 of the housing 16. It should beappreciated that the term “dwell time”, as used herein, refers to theaverage amount of time required for a molecule in the gaseous emissions10 to travel through the enlarged portion 19 of the housing 16. In otherwords, the “dwell time” of the enlarged portion 19 of the housing 16equals the amount of time it takes for all of the emissions in theenlarged chamber 21 to be renewed. It should also be appreciated thatthe term “cross-sectional area”, as used herein, refers to the internalcross-sectional area (i.e. the space inside the housing 16), whichremains the same irrespective of changes to a thickness of the housing16. Therefore, the enlarged portion cross-sectional area A₂ reflects thesize of the enlarged chamber 21 and is bounded by the interior surface68.

Due to the geometry of the housing 16, the internal pressure P₁ of thegaseous emissions 10 passing through the entry portion 18 of the housing16 and the internal pressure P₃ of the gaseous emissions 10 passingthrough the exit portion 20 of the housing 16 are greater than aninternal pressure P₂ of the gaseous emissions 10 passing through theenlarged portion 19 of the housing 16. This pressure differential incombination with the fact that the flow velocity V₂ of the gaseousemissions 10 within the enlarged portion 19 of the housing 16 is lessthan the flow velocity V₁ of the gaseous emissions 10 in the entryportion 18 of the housing 16 and is less than the flow velocity V₃ ofthe gaseous emissions 10 in the exit portion 20 of the housing 16 causesthe gaseous emissions 10 to dwell in the enlarged portion 19 of thehousing 16. As a result of the pressure and velocity differentials notedabove and because the gaseous emissions 10 will naturally expand tooccupy the entire volume of the enlarged chamber 21, an expansion forceis thus imparted on the gaseous emissions 10 in the enlarged portion 19of the housing 16. This in combination with the effects of laminar flow,pneumatic dynamics, and gas behavior physics, the resultant increase indwell time improves the ability of the reverse venturi apparatus 15 toefficiently capture and thereby remove contaminants from the gaseousemissions 10.

The housing 16 may have a variety of different shapes andconfigurations. For example and without limitation, the entry portion18, the enlarged portion 19, and the exit portion 20 of the housing 16illustrated in FIGS. 4A-D all have circular shaped cross-sectional areasA₁, A₂, A₃. Alternatively, the cross-sectional areas A₁, A₂, A₃ of oneor more of the entry portion 18, the enlarged portion 19, and the exitportion 20 of the housing 16 may have a non-circular shape, wherevarious combinations of circular and non-circular shaped cross-sectionalareas are possible and are considered to be within the scope of thesubject disclosure. In some configurations, the enlarged portion 19 ofthe housing 16 may have a divergent end 22 and a convergent end 23. Inaccordance with these configurations, the enlarged portion 19 of thehousing 16 gradually tapers outwardly from the entry portioncross-sectional area A₁ to the enlarged portion cross-sectional area A₂at the divergent end 22. In other words, the cross-section of theenlarged portion 19 of the housing 16 increases at the divergent end 22moving in a direction away from the entry portion 18 of the housing 16.By contrast, the enlarged portion 19 of the housing 16 gradually tapersinwardly from the enlarged portion cross-sectional area A₂ to the exitportion cross-sectional area A₃ at the convergent end 23. In otherwords, the cross-section of the enlarged portion 19 of the housing 16decreases at the convergent end 23 moving in a direction towards theexit portion 20 of the housing 16. Therefore, it should be appreciatedthat the gaseous emissions 10 in the enlarged portion 19 of the housing16 generally flow from the divergent end 22 to the convergent end 23. Inembodiments where the entry portion 18, the enlarged portion 19, and theexit portion 20 of the housing 16 all have circular shapedcross-sectional areas A₁, A₂, A₃, the divergent and convergent ends 22,23 of the housing 16 may generally have a conical shape.Notwithstanding, alternative shapes for the divergent and convergentends 22, 23 of the enlarged portion 19 of the housing 16 are possible.By way of example and without limitation, the divergent and convergentends 22, 23 may have a polygonal shape for improved manufacture easewhile avoiding any significant detrimental effects to the flow of thegaseous emissions 10 through the housing 16 of the reverse venturiapparatus 15. In another alternative configuration, the enlarged portion19 of the housing 16 may have a shape resembling a sausage withrelatively abrupt transitions between the entry portion 18 and thedivergent end 22 and the convergent end 23 and the exit portion 20. Itis presumed that a smooth transition is preferred to an abrupttransition because laminar flow behavior of the gaseous emissions 10 maybe preferred. However, minor disturbances to the laminar flow of thegaseous emissions 10 at abrupt transitions are not perceived to be anoverwhelming penalty, but rather may provide enhanced flow in areaswhere increased dwell time is not necessary.

With continued reference to FIGS. 4A-D and with additional reference toFIGS. 5-11, a mass of reactive material 24 is disposed within theenlarged portion 19 of the housing 16. The mass of reactive material 24has a reactive outer surface 25 that is disposed in contact with thegaseous emissions 10. In addition, the mass of reactive material 24contains an amalgam forming metal at the reactive outer surface 25 thatchemically binds at least some of the contaminants in the gaseousemissions 10 that are passing through the enlarged portion 19 of thehousing 16 to the reactive outer surface 25 of the mass of reactivematerial 24. In this way, the contaminants bound to the reactive outersurface 25 of the mass of reactive material 24 remain trapped in theenlarged portion 19 of the housing 16 and are thus removed from the flowof the gaseous emissions 10 exiting the enlarged portion 19 of thehousing 16 and entering the exit portion 20 of the housing 16. It shouldbe appreciated that the term “amalgam forming metal”, as used herein,describes a material, selected from a group of metals, that is capableof forming a compound with one or more of the contaminants in thegaseous emissions 10. By way of non-limiting example, the amalgamforming metal may be zinc and the contaminant in the gaseous emissions10 may be mercury such that an amalgam of zinc and mercury is formedwhen the gaseous emissions 10 come into contact with the reactive outersurface 25 of the mass of reactive material 24.

It should be appreciated that the enlarged portion 19 of the housing 16must be sized to accommodate the pre-determined entry flow rate of thegaseous emissions 10 while providing a long enough dwell time to enablethe amalgam forming metal in the mass of reactive material 24 tochemically bind with the contaminants in the gaseous emissions 10.Accordingly, to achieve this balance, the enlarged portioncross-sectional area A₂ may range from 3 square feet to 330 square feetin order to achieve a dwell time ranging from 1 second to 2.5 seconds.The specified dwell time is necessary to allow sufficient time for thecontaminants in the gaseous emissions 10 to chemically bind to theamalgam forming metal in the mass of reactive material 24. Thus, therange for the enlarged portion cross-sectional area A₂ was calculated toachieve this residence time for coal burning power plants 100 withoutputs ranging from 1 Mega Watt (MW) to 6,000 Mega Watts (MW). As isknown in the chemical arts, the amalgam forming metal may be a varietyof different materials. By way of non-limiting example, the amalgamforming metal may be selected from a group consisting of zinc, iron, andaluminum. It should also be appreciated that the housing 16 is made froma material that is different from the mass of reactive material 24. Byway of non-limiting example, the housing 16 may be made from steel,plastic, or fiberglass.

The mass of reactive material 24 may be provided in a variety ofdifferent, non-limiting configurations. With reference to FIG. 4A, themass of reactive material 24 is shown coating the interior surface 68 ofthe housing 16. Alternatively, with reference to FIGS. 5-11, the mass ofreactive material 24 may form one or more obstruction elements 26 a-jthat are disposed within the enlarged portion 19 of the housing 16. Assuch, the obstruction element(s) 26 a-j create a tortuous flow path 27for the gaseous emissions 10 passing through the enlarged portion 19 ofthe housing 16. Accordingly, the obstruction element(s) 26 a-j increasethe dwell time for the gaseous emissions 10 passing through the enlargedportion 19 of the housing 16. Several of the embodiments discussed belowbreak up the flow of the gaseous emissions 10 passing through theenlarged portion 19 of the housing 16 so completely that the tortuousflow path 27 created is completely random, which greatly enhances theopportunity for chemical reactions between the contaminants in thegaseous emissions 10 and the amalgam forming metal in the mass ofreactive material 24.

The obstruction element(s) 26 a-j in each of the configurations shown inFIGS. 5-11 present a large surface area, such that the reactive outersurface 25 of the mass of reactive material 24 is large. This isadvantageous because chemical reactions between the amalgam formingmetal in the reactive outer surface 25 of the mass of reactive material24 and contaminants in the gaseous emissions 10 allow the enlargedportion 19 of the housing 16 to trap, capture, and/or collect thecontaminants, thereby removing/eliminating them from the gaseousemissions 10. Accordingly, the amount of contaminants that the enlargedportion 19 of the housing 16 can remove from the gaseous emissions 10passing through the enlarged chamber 21 is proportional to the size ofthe reactive outer surface 25 of the mass of reactive material 24 in theenlarged portion 19 of the housing 16. In addition, the complex surfaceshapes and/or texture of the obstruction(s) 26 a-j can provideadditional surface area to facilitate the physical capture ofcontaminants whether the capture is the result of a chemical reactionbetween the contaminants and the amalgam forming metal or not.

Referring again to FIG. 3, the sorbent that is added to the emissions bythe sorbent injector 14 contains the amalgam forming metal. As such, theamalgam forming metal in the sorbent chemically binds with at least someof the contaminants in the gaseous emissions 10 before the gaseousemissions 10 enter the enlarged portion 19 of the housing 16. Althoughthe sorbent may have a number of different compositions, the sorbent maybe, for example, a zinc (Zn) powder or a copper, zinc, tin, sulfur(CZTS) compound. Because the sorbent chemically binds with at least someof the contaminants in the gaseous emissions 10 before the gaseousemissions 10 enter the enlarged portion 19 of the housing 16, thesorbent helps the mass of reactive material 24 remove the contaminantsfrom the gaseous emissions 10.

With reference to FIG. 5, the obstruction elements 26 a-j are providedin the form of a series of staggered baffles 26 a that extend from theinterior surface 68 of the enlarged portion 19 of the housing 16. Theseries of staggered baffles 26 a are transverse to the central axis 17and give the tortuous flow path 27 a serpentine shape. The serpentineshape of the tortuous flow path 27 increases the dwell time of thegaseous emissions 10 in the enlarged portion 19 of the housing 16, whichin turn improves the capture and removal of the contaminants in thegaseous emissions 10 by the mass of reactive material 24 forming theseries of staggered baffles 26 a. In one variation, the series ofstaggered baffles 26 a are made of zinc. In another variation, theseries of staggered baffles 26 a are made of a non-zinc material that iszinc coated. It should be appreciated that the placement of thestaggered baffles 26 a need not be equally or symmetrically orientedalong a length of the central axis 17 because some applications maybenefit from larger spaces between adjacent baffles 26 a while otherapplications may benefit from smaller spaces between adjacent baffles 26a. It should also be appreciated that the series of staggered baffles 26a can be replaced and/or cleaned as necessary if they become saturatedduring operation of the reverse venturi apparatus 15.

With reference to FIGS. 6A-B, the at least one obstruction element 26a-j is alternatively in the form of an auger-shaped baffle 26 b. Theauger-shaped baffle 26 b extends helically within the enlarged portion19 of the housing 16 along and about the central axis 17. Accordingly,the auger-shaped baffle 26 b gives the tortuous flow path 27 a spiralingshape. The spiraling shape of the tortuous flow path 27 increases thedwell time of the gaseous emissions 10 in the enlarged portion 19 of thehousing 16, which in turn improves the capture and removal of thecontaminants from the gaseous emissions 10 by the mass of reactivematerial 24 forming the auger-shaped baffle 26 b. In one variation, theauger-shaped baffle 26 b is made of zinc. In another variation, theauger-shaped baffle 26 b is made of a non-zinc material that is zinccoated. In yet another variation, the auger-shaped baffle 26 b ismechanically driven such the auger-shaped baffle 26 b rotates within theenlarged portion 19 of the housing 16 about the central axis 17.Rotation of the auger-shaped baffle 26 b can either artificiallyaccelerate or artificially slow the flow of the gaseous emissions 10through the enlarged portion 19 of the housing 16, depending upon whichdirection the auger-shaped baffle rotates. It should be appreciated thatthe auger-shaped baffle 26 b can be replaced and/or cleaned as necessaryif the auger-shaped baffle 26 b becomes saturated during operation ofthe reverse venturi apparatus 15.

With reference to FIGS. 7A-B, the at least one obstruction element 26a-j is a plurality of baffles 26 c. Each baffle 26 c extendstransversely across the enlarged portion 19 of the housing 16 from theinterior surface 68 of the enlarged portion 19 of the housing 16. Thebaffles 26 c are spaced apart from one another along the central axis 17and each baffle 26 c includes orifices 28 that permit the flow of thegaseous emissions 10 through the baffles 26 c. Of course it should beappreciated that any number of baffles 26 c are possible, including aconfiguration containing only a single baffle 26 c. It should also beappreciated that the size, shape, and number of orifices 28 in eachbaffle 26 c may vary. For example, the baffles 26 c may be provided inthe form of a screen, where the orifices 28 are formed between thecrossing wires of the screen. The orifices 28 in the baffles 26 crestrict the flow of the gaseous emissions 10 in the enlarged portion 19of the housing 16 and thus increase the dwell time of the gaseousemissions 10 in the enlarged portion 19 of the housing 16. This improvesthe capture and removal of the contaminants from the gaseous emissions10 by the mass of reactive material 24 forming the baffles 26 c. In onevariation, the baffles 26 c are made of zinc. Another variation, thebaffles 26 c are made of a non-zinc material that is zinc coated. Itshould be appreciated that the baffles 26 c can be replaced and/orcleaned as necessary if they become saturated during operation of thereverse venturi apparatus 15. In yet another variation, the size(s) ofthe orifices 28 in one of the baffles 26 c is different than the size(s)of the orifices 28 in an adjacent one of the baffles 26 c. By usingdifferent sizes of orifices 28 in different baffles 26 c, the flow ofgaseous emissions 10 can be accelerated and/or restricted to improve thecapture and removal of the contaminants in the gaseous emissions 10 bythe mass of reactive material in the baffles 26 c. In a similar way, thebaffles 26 c need not be equally spaced apart in the enlarged chamber21, nor do the orifices 28 in one of the baffles 26 c need to be thesame size, shape, or in the same location as the orifices 28 in anadjacent baffle 26 c. By taking advantage of different sizes, shapes,and locations of the orifices 28 from one of the baffles 26 c to anotherand by taking advantage of different spacing of the baffles 26 c, thedwell time of the gaseous emissions 10 in the enlarged portion 19 of thehousing 16 can be increased so as to promote increased contact with thephysical and chemical capture and collection sites along the mass ofreactive material 24.

In other alternative configurations shown in FIGS. 8-11, the at leastone obstruction element 26 a-j may not be fixed to the housing 16itself, but instead may be freely positioned inside the enlarged portion19 of the housing 16. In such configurations, the at least oneobstruction element 26 a-j may include various forms of obstructionmedia 26 d-j. Like obstruction elements 26 a-c, the obstruction media 26d-j is capable of being made from zinc or from a non-zinc material thatis zinc coated. Zinc is easily melted allowing complex shapes to be castusing normal molding methods, lost wax investment processes, centrifugalprocesses, and the like. Other construction methods will readily includemachining, extrusion, sintering, stamping, hot forging and forming,laser cutting, and the like. Alternatively, steel may be used to createan underlying shape, which is then subsequently coated or plated in zincas a surface cover. The obstruction media 26 d-j can be used tocompletely fill the entire enlarged chamber 21, partially fill theenlarged chamber 21, or fill in between the baffles 26 c previouslydescribed in connection with FIGS. 7A-B.

FIG. 8 illustrates a configuration where the at least one obstructionelement 26 a-j is a plurality of fragments 26 d that are contained inthe enlarged portion 19 of the housing 16. In accordance with thisconfiguration, the gaseous emissions 10 pass through the spaces betweenadjacent fragments 26 d as the gaseous emissions 10 travel through theenlarged portion 19 of the housing 16 from the entry portion 18 to theexit portion 20 of the housing 16. To this end, the plurality offragments 26 d may be provided with an irregular shape such that thefragments 26 d loosely pack with each other in the enlarged portion 19of the housing 16. In one non-limiting example, the plurality offragments 26 d may be made of mossy zinc. Mossy zinc is popcorn shapedzinc construction that is produced by dipping molten zinc into a coolingliquid such as water. The resulting drip of molten zinc solidifies intoa relatively small spheroidal structure with extremely high surface areato volume ratios. In addition, the surface area of the resultantstructure has a moss-like surface texture. These structures can beproduced in a range of sizes for application specific uses. Some steelprocesses can produce steel versions of complex spheroidal structuressimilar to mossy zinc, which may be zinc coated.

The loose pack nature of the plurality of fragments 26 d in FIG. 8 givesthe tortuous flow path 27 a random shape, which increases the dwell timeof the gaseous emissions 10 in the enlarged portion 19 of the housing16. This in turn improves the capture and removal of the contaminantsfrom the gaseous emissions 10 by the mass of reactive material 24forming the plurality of fragments 26 d. The plurality of fragments 26 din FIG. 8 can be replaced and/or cleaned as necessary if they becomesaturated during the operation of the reverse venturi apparatus 15.

In another alternative configuration shown in FIG. 9, the at least oneobstruction element 26 a-j is a plurality of entangled strands 26 e thatare disposed in the enlarged portion 19 of the housing 16. The pluralityof entangled strands 26 e thus form a wool-like material in the enlargedportion 19 of the housing 16. In accordance with one possibleconfiguration, the plurality of entangled strands 26 e are folded andcrumpled like steel wool to form a mass with a very large surface area.The entangled strands 26 e themselves may be of the same composition,thickness, and length or alternatively may be a mixture of differentcompositions, thicknesses, and/or lengths. In one variation, theplurality of entangled strands 26 e are made from zinc wire and arerandomly entangled to form a zinc wool. The zinc wool can be producedwith varying levels of density and/or sizes of wire so as to providespecific flow restriction capabilities. In another variation, theplurality of entangled strands 26 e are made from steel wire and arerandomly entangled to form a steel wool. The steel wool may be zinccoated. The relatively loose packed nature of the plurality of entangledstrands 26 e in FIG. 9 gives the tortuous flow path 27 a random shape,which increases the dwell time of the gaseous emissions 10 passingthrough the enlarged portion 19 of the housing 16. This in turn improvesthe capture and removal of the contaminants in the gaseous emissions 10by the mass of reactive material 24 forming the plurality of entangledstrands 26 e. It should be appreciated that the plurality of entangledstrands 26 e can be replaced and/or cleaned as necessary if they becomesaturated during operation of the reverse venturi apparatus 15.

With reference to FIG. 10, another alternative configuration isillustrated where the at least one obstruction element 26 a-j is afilter element 26 f The filter element 26 f extends transversely acrossthe enlarged portion 19 of the housing 16 relative to the central axis17. The filter element 26 f is porous such that the pores in the filterelement 26 f allow the gaseous emissions 10 to pass through the filterelement 26 f as the gaseous emissions 10 flow through the enlargedportion 19 of the housing 16 from the entry portion 18 to the exitportion 20 of the housing 16. The arrangement of the filter element 26f, which may be made of a sintered metal, gives the tortuous flow path27 a random shape, which increases the dwell time of the gaseousemissions 10 passing through the enlarged portion 19 of the housing 16.This in turn improves the capture and removal of the contaminants in thegaseous emissions 10 by the mass of reactive material 24 forming thefilter element 26 f The sintered metal of the filter element 26 f ispreferably made of zinc or a non-zinc material that is zinc coated. Itshould be appreciated that the filter element 26 f can be replacedand/or cleaned as necessary if it becomes saturated during operation ofthe reverse venturi apparatus 15.

Referring to FIG. 11, the at least one obstruction element 26 a-j isillustrated as a combination of the plurality of baffles 26 c shown inFIGS. 7A-B and a plurality of fragments 26 g-j, which have differentsizes and which are similar to the plurality of fragments 26 d shown inFIG. 8. In accordance with this alternative configuration, the pluralityof baffles 26 c and the plurality of fragments 26 g-j are disposed inthe enlarged portion 19 of the housing 16 Like in FIGS. 7A-B, theplurality of baffles 26 c illustrated in FIG. 11 extend transverselyacross the enlarged portion 19 of the housing 16 from the interiorsurface 68 of the enlarged portion 19 of the housing 16. Additionally,the plurality of baffles 26 c are spaced apart relative to one anotheralong the central axis 17 such that the baffles 26 c divide the enlargedchamber 21 into multiple sections. Orifices 28 in each of the baffles 26c permit the flow of the gaseous emissions 10 through the baffles 26 c.The plurality of fragments 26 g-j are disposed between adjacent baffles26 c (i.e. are disposed in the multiple sections of the enlarged chamber21).

As illustrated in FIG. 11 and in FIGS. 12A-D, the plurality of fragments26 g-j are form the mass of reactive material 24. The plurality offragments 26 g-j may be provided in different sizes where the pluralityof fragments 26 g-j are grouped by similar size (i.e. fragments 26 g, 26h, 26 i, and 26 j are in separate groups) and are separated fromfragments of another size by the baffles 26 c. For example, the groupsof fragments 26 g-j may be arranged such that the size of the fragments26 g-j decreases moving away from the entry portion 18 of the housing 16and toward the exit portion 20 of the housing 16. In other words, thesize of the fragments 26 g-j in the various groups may be graduated anddecreasing moving in an overall flow direction of the gaseous emissions10 in the enlarged portion 19 of the housing 16. In one variation, thefragments 26 g-j are made of zinc. For example, the fragments 26 g-j maybe formed by dripping molten zinc into a cooling liquid to create apopcorn-like structure with an exceptionally large surface area and arandom, moss-like surface texture. It should be appreciated that inanother variation, different sized fragments 26 g-j may be mixedtogether and therefore are not separated into groups based on size.

As FIGS. 13A-C illustrate, several alternative shaped obstructionelements 26 k-m are shown in the form of a loose material, which may beused in addition to or instead of the plurality of fragments 26 d and 26g-j shown in FIGS. 8 and 11. FIG. 13A illustrates an example where theobstruction 26 k forms the mass of reactive material 24 and has anasterisk-like shape, which is similar to the shape of the child's toycalled “Jacks”. FIG. 13B illustrates another example where thealternative shaped obstruction element 26 k-m is a plurality ofcrystalline flakes 261 (one shown) that form the mass of reactivematerial 24 and that may be positioned in the enlarged portion 19 of thehousing 16 like the fragments 26 d and 26 g-j shown in FIGS. 8 and 11.The crystalline flakes 261 have a shape that is similar to that of asnowflake. FIG. 13C illustrates yet another example where thealternative shaped obstruction element 26 k-m is a plurality of wirecoils 26 m (one shown) that form the mass of reactive material 24 andthat may be positioned in the enlarged portion 19 of the housing 16 likethe fragments 26 d and 26 g-j shown in FIGS. 8 and 11. It should beappreciated that obstructions 26 k and the plurality of crystallineflakes 261 may be made of zinc or a non-zinc material that is zinccoated using various processes, including without limitation, lost waxforging and 3D printing. The plurality of wire coils 26 m may be made,for example, by wrapping zinc wire around a mandrel core similar to theshape of a spring, except after winding around the mandrel core theentire coil of wrapped wire is slit along the length of the mandrel coreso that individual rings of coil are generated. It should also beappreciated that the alternative shaped obstruction elements 26 k-m mayor may not completely fill the enlarged chamber 21.

It should be appreciated that the various types of obstruction elements26 a-k described above can be mixed and matched to create variouscombinations. Examples of mixing and matching include combining one ormore baffles 26 a-c shown in FIGS. 5, 6A-B, and 7A-B with the pluralityof fragments 26 d and 26 g-j shown in FIGS. 8 and 11. Other examples ofmixing and matching include combining the plurality of entangled strands26 e shown in FIG. 9 with the plurality of fragments 26 d and 26 g-jshown in FIGS. 8 and 11. Other alternative configurations are possiblethat combine the various types of obstruction elements 26 a-k describedabove with other filter materials such as activated carbon. Activatedcarbon collects contaminants like a sponge and by surface contact.Therefore, limited quantities of activated carbon can be introduced intothe enlarged portion 19 of the housing 16 to act in conjunction with thevarious types of obstruction elements 26 a-k described above.Advantageous, the obstruction elements 26 a-k would hold the activatedcarbon in the enlarged portion 19 of the housing 16 so that theactivated carbon is disposed relatively statically throughout theenlarged chamber 21. This scenario is opposite to typical emissioncontrol systems, which release activated carbon into the flow of gaseousemissions 10. Because the activated carbon is not free to flow with thegaseous emissions a more efficient use of activated carbon is possible.Those skilled in the art will readily appreciate that the disclosedvariations of the reverse venturi apparatus 15 are merely exemplary andthat many combinations well beyond the few examples disclosed herein arepossible and desirable to address specific applications.

With reference to FIG. 14, another exemplary reverse venturi apparatus15′ is illustrated that includes two enlarged portions 19, 19′ that arejoined together in series by conduit 38. One enlarged portion 19 of thehousing 16 extends between the entry portion 18 of the housing 16 andthe conduit 38 while the other enlarged portion 19′ extends between theconduit 38 and the exit portion 20 of the housing 16. Thus, the tortuousflow path 27 for the gaseous emissions 10 is elongated. In accordancewith this configuration, the gaseous emissions 10 are routed fromenlarged portion 19 through conduit 38 and to enlarged portion 19′ whereadditional contaminants are collected and/or captured. It should also beappreciated that the subject disclosure is not limited to using just oneor two enlarged portions 19, 19′ in series, because some applicationswith an extensive volume of emissions and/or heavy contamination levelsmay require numerous enlarged portions connected together in series.

Referring to FIG. 15, another exemplary reverse venturi apparatus 15″ isillustrated that includes two enlarged portions 19, 19″ that are joinedtogether in parallel. A 3-way inlet valve 39 controls the flow ofgaseous emissions 10, directing the gaseous emissions 10 into andthrough either conduit 41 or conduit 42. A 3-way outlet valve 40 directsthe gaseous emissions 10 to exit from either conduit 41 or conduit 42without back-flowing directly from conduit 41 into conduit 42, or viceversa. The gaseous emissions 10 enter enlarged portion 19 through entryportion 18 and exit through exit portion 20 when the gaseous emissions10 are routed through conduit 41. The gaseous emissions 10 enterenlarged portion 19″ through entry portion 18″ and exit through exitportion 20″ when the gaseous emissions 10 are routed through conduit 42.One benefit of the reverse venturi apparatus 15″ shown in FIG. 15 isthat when one of the enlarged portions 19, 19″ requires maintenance,servicing, or cleaning, it can be isolated and taken off-line withoutshutting down the entire system, because the other one of the enlargedportions 19, 19″ can remains in service.

Over time, the chemical reactions occurring on the reactive outersurface 25 of the mass of reactive material 24 and/or the physicalcapture of contaminants may lead to a saturation point for the mass ofreactive material 24 wherein the efficiency of the reverse venturiapparatus 15 is reduced. The arrangement shown in FIG. 15 thereforeallows for the removal, replacement, and/or cleaning of the mass ofreactive material 24 in the enlarged portions 19, 19″ of the housing 16to restore the reverse venturi apparatus to pre-saturation efficiencyperformance without requiring a complete shutdown.

The process of contaminant removal from the saturated mass of reactivematerial will specifically depend upon the type of contaminants and thetype of amalgam forming metal being used. Access to the enlargedchambers 21, 21″, which are disposed inside the enlarged portions 19,19″ of the housing 16 will be commensurate with the type of obstructionused. When relatively small loose obstructions are used, a pouringand/or draining type access will be required. If the obstructions arerelatively large blocks, plates, baffles, or assemblies, thenappropriate lifting and handling methods and access will be required.

Still referring to FIG. 15, the reverse venturi apparatus 15 may includeone or more spray nozzles 81 that are disposed in fluid communicationwith the enlarged portions 19, 19″ of the housing 16. The spray nozzles81 are positioned to spray a deoxidizing acid over the mass of reactivematerial 24 in the enlarged portions 19, 19″ of the housing 16. Inoperation, the deoxidizing acid washes the mass of reactive material 24of the contaminants in order to rejuvenate the mass of reactive material24. Optionally, drains 82 may be disposed in fluid communication withthe enlarged portions 19, 19″ of the housing 16 to transport thesolution of used deoxidizing acid and contaminants away from theenlarged portions 19, 19″ of the housing 16. Advantageously, saturatedzinc, whether it is a coating on steel, or a solid zinc structure, canbe recycled and reclaimed. Therefore, the material used in theobstructions can be reused and reclaimed. In addition, many of thecontaminants which are captured, especially the heavy metals such asmercury, may be able to be reused and reclaimed in lighting and chlorinemanufacture.

With reference to FIG. 16, another exemplary reverse venturi apparatus15 is illustrated where the enlarged chamber 45 has a significantlylarger volume compared to the volume of entrance conduit 43 and exitingconduit 44. The enlarged portion 46 can be round, square, triangular,oval, or virtually any one of many shapes as may be desired (where arectangular shape is shown), in order to achieve an enlarged tortuousflow path 77 for the gaseous emissions flowing through the enlargedportion 46.

With reference to FIG. 17, a block diagram of a typical gaseous emissioncontrol system is shown. Gaseous emissions are routed from a furnace 47to an electrostatic precipitator (ESP) 48, and then to a fluidized gasdesulfurization (FGD) unit 49, and then through a fabric filter (FF)unit 50, before being released to atmosphere through a stack 51. A firstconcentrate 52 of contaminants is removed from the gaseous emissions atthe ESP 48. In a similar fashion, a second concentrate 53 ofcontaminants is removed from the gaseous emissions at the FGD unit 49.The second concentrate 53 produced by the FGD unit 49, which oftencontains mercury and other heavy metals, is typically diverted intowastewater. A third concentrate 54 of contaminants is removed from thegaseous emissions at the FF unit 50.

With reference to FIGS. 18A-B, the block diagram of FIG. 17 has beenmodified with introduction point options for sorbent injection and anadditional step has been added where the gaseous emissions are passedthrough the reverse venturi apparatus 15 described above. In FIG. 18A, afirst sorbent introduction point 55 is shown positioned between thefurnace 47 and the ESP 48. Alternatively, in FIG. 18B, a second sorbentinduction point 56 is shown positioned between the FGD unit 49 and theFF unit 50. Which option is deemed to be best for sorbent will bedependent upon the existing configuration and condition of the plant.There are numerous other introduction points and/or combinations ofintroduction points where the sorbent can be introduced other than thetwo options depicted in FIGS. 18A-B, therefore these two options areillustrated for demonstrative purposes. The reverse venturi apparatus 15in FIGS. 18A-B is located after the FF unit 50 and before the stack 51.The reverse venturi apparatus 15 can be constructed in accordance withany of the aforementioned examples described above, as may beappropriate for various applications. In the end, the final gaseousemissions released to atmosphere through the stack 51 after exiting thereverse venturi apparatus 15 will be capable of meeting and exceedingcurrent and future EPA emissions regulations and requirements.

The method illustrated by FIGS. 18A-B includes the steps of burning afuel in the furnace 47 to generate gaseous emissions that containcontaminants, routing the gaseous emissions from the furnace 47 to theESP 48, and removing a first portion particulate contaminants in thegaseous emissions using the ESP 48. In accordance with the step ofremoving a first portion particulate contaminants in the gaseousemissions using the ESP 48, the first concentrate 52 is formed, whichcontains the first portion of particulate contaminants that have beenremoved from the gaseous emissions by the ESP 48. It should beunderstood that in operation, the ESP 48 utilizes an inducedelectrostatic charge to remove fine contaminant particles from thegaseous emissions. The method also includes the steps of routing thegaseous emissions from the ESP 48 to the FGD unit 49 and removing sulfurdioxide contaminants in the gaseous emissions using the FGD unit 49. Inaccordance with the step of removing sulfur dioxide contaminants in thegaseous emissions using the FGD unit 49, the second concentrate 53 isformed containing the sulfur dioxide contaminants that have been removedfrom the gaseous emissions by the FGD unit 49. The method furtherincludes the steps of routing the gaseous emissions from the FGD unit 49to the FF unit 50 (i.e. a bag house) and removing a second portion ofparticulate contaminants in the gaseous emissions using the FF unit 50.In accordance with the step of removing a second portion of particulatecontaminants in the gaseous emissions using the FF unit 50, the thirdconcentrate 54 is formed containing the second portion of particulatecontaminants that have been removed from the gaseous emissions by the FFunit 50. It should be understood that in operation, contaminantparticles are removed from the gaseous emissions when the gaseousemissions pass through the one or more fabric filters (not shown) of theFF unit 50.

In accordance with the subject disclosure, the method further includesthe steps of routing the gaseous emissions from the FF unit 50 to thereverse venturi apparatus 15 and removing heavy metal contaminants inthe gaseous emissions using the reverse venturi apparatus 15. Inaccordance with the step of removing heavy metal contaminants in thegaseous emissions using the reverse venturi apparatus 15, the gaseousemissions pass by (i.e. flow over) the mass of reactive materialdisposed in the reverse venturi apparatus 15. The amalgam forming metalin the mass of reactive material chemically binds with the heavy metalcontaminants in the gaseous emissions. Accordingly, the mass of reactivematerial traps the heavy metal contaminants in the reverse venturiapparatus 15 when the heavy metal contaminants bind to the amalgamforming metal in the mass of reactive material. The method may thenproceed with routing the gaseous emissions from the reverse venturiapparatus 15 to a stack 51 that vents the gaseous emissions to thesurrounding atmosphere. It should also be appreciated that the reverseventuri apparatus 15 advantageously has a relatively small equipmentfootprint, allowing it to be easily installed as a retrofit in linebetween the emission control devices 48, 49, 50 of existing systems andthe stack 51 to atmosphere.

Optionally, the method may include the step of injecting a sorbent intothe gaseous emissions. In accordance with this step and as shown in FIG.18A, the sorbent may be injected into the gaseous emissions at the firstsorbent introduction point 55 that is disposed between the furnace 47and the ESP 48. Alternatively, as shown in FIG. 18B, the sorbent may beinjected into the gaseous emissions at the second sorbent introductionpoint 56 that is disposed between the FGD unit 49 and the FF unit 50.The sorbent contains the amalgam forming metal such that the sorbentbinds with at least some of the heavy metal contaminants in the gaseousemissions before the gaseous emissions enter the reverse venturiapparatus 15. By injecting the sorbent into the gaseous emissions at thefirst sorbent introduction point 55 or the second sorbent introductionpoint 56, more mercury, heavy metals, and acid gasses can be collectedin the FF unit 50 at levels that were previously impossible to achieve.As noted above, the amalgam forming metal may be selected from a groupconsisting of zinc, iron, and aluminum and the sorbent may be, forexample, a CZTS compound. The sorbent is able to be regenerated andrejuvenated so that the hazardous contaminants can be harvested andrecycled.

With reference to FIG. 19, a block diagram of a typical non-gaseousemission control system is shown. Liquid and/or liquid-like emissionscan be routed from a fluidized gas desulfurization (FGD) unit 59 and/orrouted from a wet scrubber unit 58 into a lime treatment unit 60 beforebeing routed to a settling pond 61. After an appropriate period of time,the non-gaseous emissions will be routed out of the settling ponds 61into either a process system for dry disposal preparation 64 or to adewatering system 62. The non-gaseous emissions that are routed throughthe process for dry disposal 64 are prepared for disposal in a landfill65. The non-gaseous emissions that are routed through the dewateringsystem 62, which sometimes may include a recirculation system, areprepared for use in a secondary industrial process 63, which forexample, may involve the manufacture of gypsum and/or cement. Thenon-gaseous emissions that are not routed out the settling ponds 61 intothe dewatering systems 62 or into the processes for dry disposal 64 arerouted for discharge into waterways 66. The final non-gaseous emissionsreleased into the waterways 66 are not as regulated as they will be incoming years. The proposed EPA water emissions regulations andrequirements will be extraordinarily restrictive compared to theemissions allowed into waterways at the present time. The industrieswith contaminated liquid emissions requiring discharge into waterwayshave current emissions control technology which has virtually nopossibility of meeting and/or complying with the coming EPA regulations.

With reference to FIG. 20, the block diagram of FIG. 19 has beenmodified with one or more treatment tanks 67, which contain the sorbentdescribed above. The treatment tanks 67 are located after thenon-gaseous emissions are routed out of the settling pond 61 and beforethey are discharged into the waterways 66. The method illustrated byFIG. 20 includes the steps of collecting non-gaseous emissions thatcontain contaminants, passing the non-gaseous emissions through the FGDunit 59 and/or the wet scrubber 58 to remove some of the contaminants inthe non-gaseous emissions, routing the non-gaseous emissions from theFGD unit 59 and/or the wet scrubber 58 to a lime treatment unit 60, andpassing the non-gaseous emissions through the lime treatment unit 60 tosoften the non-gaseous emissions through Clark's process. It should beunderstood that in operation, the lime treatment unit 60 removes certainions (e.g. calcium (Ca) and magnesium (Mg)) from the non-gaseousemissions by precipitation. The method also includes the steps ofrouting the non-gaseous emissions from the lime treatment unit 60 to thesettling pond 61 where some of the contaminants in the non-gaseousemissions are removed by sedimentation, dewatering a first portion ofthe non-gaseous emissions in the settling pond 61 and using thedewatered by-product in a secondary industrial process 63, and removinga second portion of the non-gaseous emissions from the settling pond 61and subjecting the second portion of the non-gaseous emissions to a drydisposal process 64. In accordance with the step of dewatering the firstportion of the non-gaseous emissions in the settling pond 61 and usingthe dewatered by-product in the secondary industrial process 63,dewatering process may include recirculation of the first portion of thenon-gaseous emissions and the secondary industrial process 63 mayinvolve, for example, the manufacture of gypsum or the manufacture ofcement. In accordance with the step of removing the second portion ofthe non-gaseous emissions from the settling pond 61 and subjecting thesecond portion of the non-gaseous emissions to the dry disposal process64, the dry disposal process 64 may include depositing the secondportion of the non-gaseous emissions in the landfill 65.

In accordance with the subject disclosure, the method further includesthe step of routing a third portion of the non-gaseous emissions in thesettling pond 61 to the treatment tanks 67 containing the disclosedsorbent. The sorbent contains an amalgam forming metal that binds withheavy metal contaminants in the third portion of non-gaseous emissions.Accordingly, the sorbent traps the heavy metal contaminants in thetreatment tanks 67 when the heavy metal contaminants bind with thesorbent and settle/precipitate out of the non-gaseous emissions. Themethod may then proceed with routing the non-gaseous emissions from thetreatment tanks 67 to the waterway 66 for discharge. It should beappreciated that the design of the treatment tanks 67 may allow thecontinuous passage of the non-gaseous emissions (i.e. the wastewaterstream) through the treatment tanks 67.

With respect to the sorbent of the subject disclosure, several exemplaryembodiments are disclosed. These exemplary embodiments are just a fewexamples and do not represent an exhaustive list of potential variationson the theme.

As noted above, one exemplary sorbent is elemental zinc powder. Zincpowder is made from elemental zinc. Zinc can come in the form of powdersor in the form of granules. One method that can be used to extend theeffective life of the zinc powder and/or granules at elevatedtemperatures for some gaseous emission applications and reduce and/orprevent premature oxidation is to mix or coat the granules and/or powderwith a solid acid such as sulfamic acid, citric acid, or other organicacids. The powder/acid mixture can be injected into gaseous emissions(e.g. flue gas streams) and/or placed in an appropriate exemplaryembodiment of the reverse venturi apparatus 15.

Optimal particle size for the zinc powder ranges from 0.5 nanometers to7,500 microns. In addition, it has been found that a powder mixture witha range of different size particles is beneficial, especially if theparticle sizes range from 0.5 nanometers to 7,500 microns. Similarly,the optimal particle size for zinc granules ranges from 7,500 microns to3.0 inches. In addition, it has been found that a granule mixture with arange of different size granules is beneficial, especially if thegranule sizes range from 7,500 microns to 3.0 inches.

In another exemplary embodiment, the sorbent is CZTS, which has theelemental formula of Cu₂ZnSnS₄. CZTS may also include other phases ofcopper, zinc, tin, and sulfur, which are also beneficial. CZTS and/orthe associated phases of copper, zinc, tin, and sulfur may be blended instoichiometric proportions and then mechanochemical compounding may beperformed in a mill. Further still, the CZTS may be blended with equalproportions of any one of several clays such as bentonite or zeolite andcalcium hydroxide (CaOH). The optimal particle size for CZTS powderranges from 0.5 nanometers to 7,500 microns. It has been found intesting and development that CZTS powder mixtures with a range ofdifferent size particles is beneficial, especially if the particle sizesranges from 0.5 nanometers to 7,500 microns. In applications wherespecialized CZTS granules are preferred, the optimal granule size hasbeen found to range from 7,500 microns to 3.0 inches. In addition, ithas been found that CZTS granule mixtures with a range of different sizegranules is beneficial, especially if the size of the granules rangesfrom 7,500 microns to 3.0 inches.

For most contaminants, the CZTS is most efficient at the smallestparticle size within the above stated ranges and when the highest amountof CZTS in the metallic phase is present. It should be appreciated thatduring the manufacture of CZTS, a complete transformation of the mixtureof copper, zinc, tin, and sulfur to CZTS does not take place, but is amixture of phases (e.g. danbaite (CuZn₂) and tin sulfur (SnS)).

In one exemplary manufacturing method for CZTS, copper, zinc, tin, andsulfur are added to a mill in no particular order. Milling isaccomplished using either a ball mill or some type of attrition mill ora combination of milling equipment which in sequential combinationachieve the desired particle size. Exemplary starting particle sizeranges from 325 standard mesh screens to 100 standard mesh screens,where 1 standard mesh screen equals 7,500 microns. The receivedparticles are further weighed in a predetermined molar ratio ofcopper:zinc:tin:sulfur=1.7:1.2:1.0:4.0. After confirming mesh size andmolar ratio, the particles are mechanochemically compounded into CZTSand its other phases by milling. Milling time is controlled to achieveoptimum properties for specific applications. It should also beappreciated that milling can be accomplished using a wet milling processby adding a suitable solvent such as glycol ether, ethylene glycol,ammonia, or other alcohols or by dry milling, which is performed in aninert gas atmosphere.

During the milling, intermittent sampling takes place to determineparticle size using a particle size analyzer, and an SEM, XRD, or Ramanto determine percent phase transformation. The mill ball size isimportant and has been shown in testing to be optimized with aball-to-powder weight ratio (charge ratio) of at least 5:1. The millingballs are best made of steel, ceramic, zirconia or any other materialwhich achieves the size and/or phase transformations withoutcontaminating the final product. When wet milling is used, the CZTS isdried. The CZTS is then blended further using a ribbon blender,V-blender, or any other suitable blender in order to blend in equalportions of bentonite or zeolite and calcium hydroxide.

In accordance with the methods described above, the sorbent may beintroduced into gaseous emissions where the gaseous emissions are at atemperature of approximately 750 degrees Fahrenheit or less. The sorbentmay be introduced into the gaseous emissions by any one of severalmethods such as, but not limited to, injection, fluid beds, coatedfilters, and traps. The method of introduction can be chosen based onexisting emissions control systems in the plant to facilitateretro-fitting. One convenient method may be where CZTS is injected intothe gaseous emissions in place of activated carbon, where the sameinjection equipment may be used with or without modification.

In some applications, the treatment of gaseous emissions may beoptimized when CZTS is blended with bentonite for effective contaminantremoval. Alternatively, the treatment of non-gaseous emissionapplication may be optimized when CZTS is blended with Zeolite. Inaddition to the specific material blended with CZTS, the proportions ofthe blend may be application specific in order to provide optimizedcontaminant removal capabilities.

As shown in FIGS. 18A-B, where CZTS is used to treat gaseous emissions,the fabric filter unit 50 should be placed downstream of the CZTSintroduction point 55, 56 so that the fabric filter unit 50 capturessorbent particles and increases the contact time that the gaseousemissions have with the sorbent. Deposition of the sorbent on the fabricfilters (i.e. bags) of the fabric filter unit 50 allows additionalcontact time between the gaseous emissions and the sorbent and allowsthe sorbent to be collected for subsequent reclamation. The smallparticle size of the sorbent allows the sorbent to be carried along inthe flow of gaseous emissions stream like dust being carried by thewind. During the period of time that the sorbent is carried in the flowof gaseous emissions, the sorbent comes in contact with contaminantsalso traveling in the flow of gaseous emissions and thusly canchemically react with and bind to the sorbent. Upon reaching the fabricfilter unit 50, the gaseous emissions continue to pass through thefilters in the fabric filter unit 50 while the particles of combinedsorbent and contaminants are sized too large to pass through thefilters. When the CZTS particles are less than 10 microns, it may benecessary to pre-coat the filters in the fabric filter unit 50 with alarger size CZTS particle, activated carbon, talc, lime, or otherappropriate substance so the smaller CZTS particles do not pass throughthe filters. Alternative, a lower micron size rated filter may be usedin the fabric filter unit 50.

In other applications for non-gaseous emissions, CZTS may be introducedinto the treatment tanks 67 illustrated in FIG. 20. In thisconfiguration, the CZTS is optimally introduced into the treatment tanks67 with good agitation for a period of time, then the non-gaseousemissions (e.g. wastewater) undergoes pH adjustment, flocculation, andfiltering before discharge. Afterwards, the CZTS in the treatment tanks67 can undergo a reclamation process where the contaminants areharvested away from the CZTS. Used CZTS can be reclaimed by eitherleaching mercury from the CZTS or by vacuum distillation. The harvestedcontaminants may then be re-used in other industries. The CZTS alsoprovides the benefit of being able to reduce nitrate and nitride levelsin the non-gaseous emissions.

The water discharge regulations established by the EPA, which becomeeffective in 2016, are much more stringent than those for air. Some ofthe current EPA water regulation levels listed in nanograms/Liter(ng/L), micrograms/Liter (μg/L), and/or grams/Liter are: mercury @ 119ng/L; arsenic (As) @ 8 μg/L; selenium (Se) @ 10 μg/L; nitrogen dioxide(NO₂) and nitrate (NO₃) @ 0.13 g/L. Other heavy metals such as lead (Pb)and cadmium (Cd) also have proposed EPA restrictive levels. In manyexisting plants, water with contamination levels above allowabledischarge regulations are routed to holding ponds and/or other types ofsludge holding reservoirs of one kind or another. CZTS can treat solidsin holding ponds by the same methods as disclosed herein for treatingnon-gaseous emissions. Depending on the ionic form of the heavy metal,sludge composition, and/or pH, the contact time for the CZTS in theholding pond can be appropriately adjusted. Adequate pH adjustment,flocculation, and subsequent filtering will allow for normal discharge,disposal, and/or use in other industries, none of which was previouslypossible.

It should be appreciated that the sorbents disclosed herein do notcontain any loose carbon, including the activated carbon currently usedin the art. As a result, none of the metal sulfides produced asby-products of the disclosed methods are leachable. Therefore, theseby-products have valuable industrial use in gypsum wallboard and cementapplications. EPA leach testing on metal sulfides is well known and usein these products is well documented.

Although activated carbon may be used in some alternativeconfigurations, the limited use of activated carbon in these variationsdoes not allow for the activated carbon to escape into the emissions.For example, in one configuration, activated carbon may be embedded inthe filters of the fabric filter unit 50. This activated carbon is notfree to escape into the flow of gaseous emissions. Another limited useof activated carbon is possible where the activated carbon coats theCZTS in its crystalline form, producing CZTS with a thin layer of carbonon the order of 1.0 nanometer in thickness or less. This helps toencourage the capture of extraordinarily small metallic vapor particlesof mercury. In a similar fashion, the CZTS crystalline form can becoated with a nanometer-like thin layer of zeolite or other coatings tospecifically target a specific hazardous contaminant for specializedapplications. Again, the activated carbon in this example is not free toescape into the flow of gaseous emissions. In another configurationshown in FIG. 33, the reverse venturi fluidized bed apparatus includesprovisions for cleaning and recycling the sorbent in the form of aseries of sorbent recycling subsystems for CZTS sorbents, CZTS-Alloysorbents, and/or CZTS-Mixture sorbents. Such CZTS-Mixture sorbents mayinclude, but are not limited to granulated iron oxide (GFO) coated withCZTS and carbon-based sorbents coated with CZTS.

Referring to FIG. 21, a graph illustrates the percentages ofcontaminants removed from emissions as a result of existing emissionscontrol systems and the reverse venturi apparatus and the methoddisclosed herein. A 90% contaminant removal level 78 is currentlyestablished for gaseous emissions by the EPA. Existing emissions controlsystems 79 are effective to remove between 88%-90% of hazardouscontaminants. However, the EPA has been raising the minimum percentagecontaminant removal required over the years to the point that manyexisting emissions control systems are no longer able to meet therequirements and many other existing emissions control systems just meetthe requirements while operating at their maximum removal capabilitiesavailable under the current technology.

Still referring to FIG. 21, the exemplary emissions control system 80may either be a new emissions control system based upon the reverseventuri apparatus, the sorbents, and/or methods disclosed herein or itmay be an existing emissions control system which has been modified andaugmented to include the reverse venturi apparatus, the sorbents, andmethods disclosed herein. Testing has confirmed that the exemplaryemissions control system 80 is effective and capable of removing atleast 98% of hazardous contaminants, which is well above the current EPAregulated levels.

Referring to FIG. 22 and FIG. 24, an exemplary method of emissionscontrol is illustrated with contaminated gaseous source 150 introducedinto the system through one or more pre-fluidized bed filters 151,through fluidized bed 152, through one or more post fluidized bedfilters 153, and through a system discharge 154, which releases thegaseous discharge with an environmentally controlled release through astack 155. It should be appreciated that it is not always necessary tofirst pass contaminated gaseous source 150 through one or morepre-fluidized bed filters 151; however, application specificrequirements may dictate the need for one or more pre-fluidized bedfilters 151.

Fluidized bed 152 has a reverse venturi shape, which has a specificlength L to diameter D size ratio of between 2.9:1 as a minimum and9.8:1 as a maximum. This ratio is optimized for extended residence flowtime of contaminated gaseous source 150 in fluidized bed 152, which isfilled with specialized sorbent such as reactive material 164. Reactivematerial 164 is a sorbent including a copper, zinc, tin, sulfur (CZTS)compound and/or an alloy thereof. The preferred exemplary length L todiameter D ratio for fluidized bed 152 is 4.4:1, which has beendetermined through trial and error testing.

Preferably, the fluidized bed 152 has a predominately round crosssection. While not shown in FIG. 24, one or more of the various bafflesand/or other application specific flow restriction obstacles disclosedherein can be incorporated into the fluidized bed 152. Fluidized bed 152also features predominately outward extending convex ends 168 and 169 topromote extended residence flow time with minimized turbulent flowthrough reactive material 164. As contaminated gaseous source 150 flowenters fluidized bed 152 at entry port 165, intimate contact withreactive material 164 is initiated, resulting in random non-turbulentflow 166. Random non-turbulent flow 166 is turned back upon itself dueto predominately outward extending convex ends 168 and 169, resulting inextended residence time in fluidized bed 152 before the non-turbulentflow 166 exits from fluidized bed 152 through exit port 167. Reactivematerial 164 promotes random non-turbulent flow 166, which is arandomized torturous flow path for contaminated gaseous source 150. Itshould be appreciated that length L of the fluidized bed 152 is notinclusive of the convex ends 168 and 169.

Fluidized bed 152 has a side outlet port 170 leading to a sorbentcleaning station 156. Sorbent cleaning station 156 has an option toremove exhausted sorbent 157 from the system for disposal. In addition,captured contaminated elements 158 captured from contaminated gaseoussource 150 by reactive material 164 and separated from reactive material164 in sorbent cleaning station 156 can be disposed and/or recycled.Sorbent cleaning station 156 returns cleaned reactive material 164 backto fluidized bed 152 through sorbent return port 159. Bulk refillsorbent container 168 provides a makeup volume of reactive material 164as necessary to replace removed exhausted sorbent 157. System discharge154 provides a gaseous discharge through an environmentally controlledrelease out of exhaust stack 155. Additional discharge of captured waste160 may also be provided by additional sorbent recycling subsystems(FIG. 33).

Referring to FIG. 23 and FIG. 24, an exemplary method of emissionscontrol is illustrated with contaminated non-gaseous source 161introduced into the system through one or more pre-fluidized bed filters151, through fluidized bed 152, through one or more post fluidized bedfilters 153, and through a system discharge 154, which releases thenon-gaseous discharge with an environmentally controlled release 162. Itshould be appreciated that it is not always necessary to first passcontaminated non-gaseous source 161 through one or more pre-fluidizedbed filters 151; however, application specific requirements may dictatethe need for one or more pre-fluidized bed filters 151.

Fluidized bed 152 has a reverse venturi shape which has a specificlength L to diameter D size ratio of between 2.9:1 as a minimum and9.8:1 as a maximum, which is optimized for extended residence flow timeof contaminated non-gaseous source 161 in fluidized bed 152, which isfilled with specialized sorbent such as reactive material 164. Reactivematerial 164 is a sorbent including a copper, zinc, tin, sulfur (CZTS)compound and/or an alloy thereof. The preferred exemplary length L todiameter D ratio for fluidized bed 152 is 4.4:1, which has beendetermined through trial and error testing.

Preferably, the fluidized bed 152 also features predominately outwardextending convex ends 168 and 169 to promote extended residence flowtime with minimized turbulent flow through reactive material 164. Ascontaminated non-gaseous source 161 flow enters fluidized bed 152 atentry port 165, intimate contact with reactive material 164 isinitiated, resulting in random non-turbulent flow 166. Randomnon-turbulent flow 166 is turned back upon itself due to predominatelyoutward extending convex ends 168 and 169 resulting in extendedresidence time in fluidized bed 152 before exiting from fluidized bed152 through exit port 167. Reactive material 164 promotes randomnon-turbulent flow 166, which is a randomized torturous flow path forcontaminated non-gaseous source 161. It should be appreciated thatlength L of the fluidized bed 152 is not inclusive of the convex ends168 and 169.

Preferably, the fluidized bed 152 has a predominately round crosssection. While not shown in FIG. 24, one or more of the various bafflesand/or other application specific flow restriction obstacles disclosedherein can be incorporated into the fluidized bed 152. Fluidized bed 152has a side outlet port 170 leading to a sorbent cleaning station 156.Sorbent cleaning station 156 has an option to remove exhausted sorbent157 from the system for disposal. In addition, captured contaminatedelements 158 captured from contaminated non-gaseous source 161 byreactive material 164 and separated from reactive material 164 insorbent cleaning station 156 can be disposed and/or recycled. Sorbentcleaning station 156 provides return to cleaned reactive material 164back to fluidized bed 152 through sorbent return port 159. Bulk refillsorbent container 168 provides makeup volume of reactive material 164 asnecessary to replace removed exhausted sorbent 157. System discharge 154provides a non-gaseous discharge through an environmentally controlledrelease 162. Additional discharge of captured waste 163 is alsoprovided.

Referring to FIG. 25, an exemplary method is shown for passingcontaminated gaseous emissions 250 through one or more pre-filters 251,through the fluidized bed 253, through one or more post filters 255,through system discharge 256, and finally released as a controlledrelease gaseous emission through exhaust stack 257 and/or through awaste disposal process 262. The fluidized bed 253 is bisected bylongitudinal plane 290. Entry port P3 and exit port P4 are configured toreceive and discharge the gaseous emissions when the fluidized bed 253is positioned with longitudinal plane 290. Obstructions (not shown)interior to fluidized bed 253 provide a preferred torturous flow pathparticularly well suited for gaseous emissions when introduced throughentry port P3 and discharged through exit port P4. The entry port P3 andthe exit port P4 are positioned above the longitudinal plane 290 of thefluidized bed 253.

As shown in FIG. 25, the fluidized bed 253 can be mounted on truck 254and is configured to tilt the fluidized bed 253 about a pivot point 252.When gaseous emissions are to be processed in the fluidized bed 253, thelongitudinal plane 290 of the fluidized bed 253 is substantiallyhorizontal. Sorbent cleaning station 258 is provided in fluidcommunication with outlet port P5 of the fluidized bed 253, wherecontaminated particles captured by the sorbent are removed. Removedcontaminates can be recycled or disposed of through station 261.Exhausted Sorbent is disposed of through station 259 and the cleanedsorbent is recycled back to the fluidized bed 253 through return port P6from sorbent return station 260.

Referring to FIG. 26, an exemplary method is shown for passingcontaminated non-gaseous emissions 295 through one or more pre-filters251, through the fluidized bed 253, through one or more post filters255, through system discharge 256, and finally released as a controlledenvironmental non-gaseous release 273 and/or through a waste disposalprocess 274. Entry port P2 and exit port P1 are configured to receiveand discharge the non-gaseous emissions. Obstructions (not shown)interior to fluidized bed 253 provide a preferred torturous flow pathparticularly well suited for non-gaseous emissions when introducedthrough entry port P2 and exit port P1. The entry port P2 and the exitport P1 are bisected by the longitudinal plane 290 of the fluidized bed253 (i.e. are aligned with longitudinal plane 290 of the fluidized bed253).

When non-gaseous emissions are to be processed in the fluidized bed 253,the longitudinal plane 290 of the fluidized bed 253 is substantiallyvertical. Sorbent cleaning station 258 is provided in fluidcommunication with outlet port P5 of the fluidized bed 253, wherecontaminated particles captured by the sorbent are removed. Removedcontaminates can be recycled or disposed of through station 261.Exhausted Sorbent is disposed of through station 259 and the cleanedsorbent is recycled back to the fluidized bed 253 through return port P6from sorbent return station 260.

Referring to FIG. 27, a matrix is shown wherein the disclosed preferredreactive CZTS Alloy sorbents 341 are compared to other sorbents,including Activated Carbon 342 and Zeolite 343. Contaminates 367 arelisted as predominate types, including Nitrogen 368, Phosphates 369,Heavy Metals 370, Sulfur 371, Mercury 372, and Selenate 373.Contaminates 367 are further listed with each sorbent enumerated ingaseous emissions 344, 346, and 348 compared to non-gaseous emissions345, 347, and 349.

The reactive CZTS Alloy sorbents 341 are confirmed by testing to beeffective in the capture and removal of contaminates 367 in gaseous 344emissions and/or non-gaseous 345 emissions. In contrast, ActivatedCarbon 342 is not effective in the capture or removal of contaminates367 in gaseous emissions 346 and/or non-gaseous emissions 347.Similarly, Zeolite 343 is not effective in the capture or removal ofcontaminates 367 in gaseous emissions 348 and/or non-gaseous emissions349.

Referring to FIG. 28, an expanded list of sorbents is shown includingthe reactive CZTS Alloy sorbents 351 of the subject disclosure and othersorbents, including Caustics 350, Ferric Oxide 355, and Zeolite 356. Thereactive CZTS Alloy sorbents 351 include a CZTS Alloy of Sulfur (S) 352,a CZTS Alloy of Selenate (S) 353, and a CZTS Alloy of Ferrous Oxide 354.The CZTS Alloy sorbents 351 collectively react effectively with thefollowing groups of contaminates: Selenate 357, Total Ionized Sulfurs358, Total Ionized Nitrogens 359, and Total Ionized Phosphates 360. Thereactive CZTS Alloy sorbents 351 are able to capture and remove thesecontaminates from both gaseous and non-gaseous emissions.

In contrast, Caustics 350 are only effective with Total Ionized Sulfurs358. Ferric Oxide 355 is only effective with Selenate 357 and has veryslow reactive characteristics with Total Nitrogens 359 and Total IonizedPhosphates 360 (and work with non-gaseous emissions only). Zeolite 356is only effective with Total Ionized Nitrogens 359 and Total IonizedPhosphates 360. As a result, known sorbents such as Caustics 350, FerricOxide 355, and Zeolite 356 have limited effective characteristicscompared to the broad-spectrum characteristics of the reactive CZTSAlloy sorbents 351 disclosed herein. Even when known sorbents have alevel of effectiveness, they all fall short of the effectiveness levelof the reactive CZTS Alloy sorbents 351 disclosed herein.

Referring to FIG. 29, matrix 364 shows the capability of prior artsorbents 365 to be post processed after being used in emissions controlsystems to capture and remove contaminates 367 including Nitrogens 368,Phosphorous 369, Heavy Metals 370, Sulfurs 369, Mercury 372, andSelenates 373. The capability to separate these contaminates 367 fromthe prior art sorbent in gaseous emissions 374 and/or non-gaseousemissions 375 is very poor and virtually non-existent except forNitrogens 368 in gaseous emissions 374. Similarly, matrix 364 shows thecapability to reuse the prior art sorbents 366 after separation ofcontaminates 367 is also virtually non-existent except for gaseousemissions 376 containing Nitrogens 368.

Referring to FIG. 30, matrix 378 shows the capability of the reactiveCZTS Alloy sorbents 339 disclosed herein to be post processed afterbeing used in emissions control systems capture and remove contaminates367 including Nitrogens 368, Phosphorous 369, Heavy Metals 370, Sulfurs369, Mercury 372, and Selenates 373. The capability to separatecontaminates 367 in gaseous emissions 374 and/or non-gaseous emissions375 emissions from the disclosed reactive CZTS Alloy sorbents 339 isparticularly advantageous because it means the contaminates 367 can bemore readily disposed of or recycled and because the reactive CZTS Alloysorbents 339 can be reused in emissions control systems (as shown inmatrix 378). Specifically, matrix 378 shows the capability to reuse thereactive CZTS Alloy sorbents 340 disclosed herein after they areseparated from contaminates 365 in gaseous emissions 376 and non-gaseousemissions 377.

Referring to FIG. 31, a block diagram shows a system and method forremoving contaminates from gaseous emissions 250. Gaseous emissions 250are monitored and analyzed in step 379 to determine the types and levelsof contaminates in the gaseous emissions 250. Monitoring can besystematic intermittent spot checks at periodic intervals or continuousin-line monitoring and analysis. Based on the types and/or levels ofcontaminates resident in the gaseous emission 250 determined by step379, emissions flow is routed through pre-filter inlet manifold 380 sothat the gaseous emissions 250 are further routed through appropriatepre-filters 381, 382, 383, and/or 384. Selection of the appropriatepre-filters 381, 382, 383, and/or 384 is accomplished through theselection method illustrated in FIG. 28.

The pre-filters shown in FIG. 31 are filled with the reactive CZTS Alloysorbents 351 shown in FIG. 28. For example, pre-filter 381 is filledwith the CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Pre-filter 382is filled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28.Pre-filter 383 is filled with the CZTS Alloy of Ferrous Oxide 354 shownin FIG. 28. Pre-filter 384 is filled with a combination of CZTS Alloysorbents 352, 353, and/or 354. Additional pre-filters can be added topre-filter inlet manifold 380, each filled with a different combinationof CZTS Alloy sorbents 352, 353, and/or 354, combined to effectivelytreat specific levels and/or types of contaminates resident in gaseousemissions 250.

After contaminated gaseous emissions 250 are routed through appropriatepre-filters, pre-filter outlet manifold 385 routes emissions intofluidized bed 253. For gaseous emissions 250, the housing of thefluidized bed 253 is arranged in an orientation that is substantiallyparallel to platform 271. Contaminates are separated from the sorbent instep 258 and returned to the fluidized bed 253 through sorbent returnport 260.

After gaseous emissions 250 exit fluidized bed 253, post-filtermonitoring step 386 determines the new levels and/or types ofcontaminates remaining in the gaseous emissions 250 and routes thegaseous emissions 250 through post-filter inlet manifold 387. Selectionof the appropriate post-filters 388, 389, 390, and/or 391 isaccomplished through the selection method illustrated in FIG. 28. Thepost-filters shown in FIG. 31 are filled with the reactive CZTS Alloysorbents 351 shown in FIG. 28. For example, post-filter 388 is filledwith the CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Post-filter 389is filled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28.Post-filter 390 is filled with the CZTS Alloy of Ferrous Oxide 354 shownin FIG. 28. Post-filter 391 is filled with a combination of CZTS Alloysorbents 352, 353, and/or 354. Post-filter outlet manifold 392 routesthe gaseous emissions 250 to gaseous system discharge 256 a where someof the gaseous emissions 250 are expelled through controlled gaseousrelease stack 257 and some of the gaseous emissions 250 are expelledthrough a proper waste disposal step 262.

Additional post-filters can be added to post-filter inlet manifold 387,each filled with a different combination of CZTS Alloy sorbents 352,353, and/or 354, combined to effectively treat specific levels and/ortypes of contaminates resident in gaseous emissions 250.

All the pre-filters 381, 382, 383, 384 and post-filters 388, 389, 390,391 can be separately routed through sorbent cleaning step 258 andsorbent return port 260. Step 258 includes separating contaminates fromthe CZTS Alloy sorbents 351 so that the contaminates can be recycledand/or properly collected for disposal 261. Any exhausted CZTS Alloysorbent 351 can be disposed through disposal step 259. Replacement ofspecific CZTS Alloy sorbents 351 to each specific pre-filter 381, 382,383, 384 and/or post-filter 388, 389, 390, 391 may be implemented afterstep 258. Specific routing diagrams and/or schematics for routingsorbent from the pre-filters 381, 382, 383, 384 and/or post-filters 388,389, 390, 391 to and from the sorbent cleaning step 258 is not shown.

Referring to FIG. 32, a block diagram shows a system and method forremoving contaminates from non-gaseous emissions 295. Non-gaseousemissions 295 are monitored and analyzed in step 379 to determine thetypes and levels contaminates in the non-gaseous emissions 295.Monitoring can be systematic intermittent spot checks at periodicintervals and/or continuous in-line monitoring and analysis. Based onthe types and/or levels of contaminates resident in the non-gaseousemission 295 determined by step 379, emissions flow is routed throughpre-filter inlet manifold 380 so that the non-gaseous emissions 295 arefurther routed through appropriate pre-filters 381, 382, 383, and/or384. Selection of the appropriate pre-filters 381, 382, 383, and/or 384is accomplished through the selection method illustrated in FIG. 28.

The pre-filters shown in FIG. 32 are filled with the reactive CZTS Alloysorbents shown in FIG. 28. For example, pre-filter 381 is filled withthe CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Pre-filter 382 isfilled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28.Pre-filter 383 is filled with the CZTS Alloy of Ferrous Oxide 354 shownin FIG. 28. Pre-filter 384 is filled with a combination of CZTS Alloysorbents 352, 353, and/or 354. Additional pre-filters can be added topre-filter inlet manifold 380, each filled with a different combinationof CZTS Alloy sorbents 352, 353, and/or 354, combined to effectivelytreat specific levels and/or types of contaminates resident innon-gaseous emissions 295.

After contaminated non-gaseous emissions 295 are routed throughappropriate pre-filters, pre-filter outlet manifold 385 routes emissionsinto fluidized bed 253. For non-gaseous emissions 295, the housing ofthe fluidized bed 253 is arranged in an orientation that issubstantially perpendicular to platform 271. Contaminates are separatedfrom the sorbent in step 258 and returned to the fluidized bed 253through sorbent return port 260.

After non-gaseous emissions 295 exit fluidized bed 253, post-filtermonitoring step 386 determines the new levels and/or types ofcontaminates remaining in the non-gaseous emissions 295 and routes thenon-gaseous emissions 295 through post-filter inlet manifold 387.Selection of the appropriate post-filters 388, 389, 390, and/or 391 isaccomplished through the selection method illustrated in FIG. 28. Thepost-filters shown in FIG. 32 are filled with the reactive CZTS Alloysorbents 351 shown in FIG. 28. For example, post-filter 388 is filledwith the CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Post-filter 389is filled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28.Post-filter 390 is filled with the CZTS Alloy of Ferrous Oxide 354 shownin FIG. 28. Post-filter 391 is filled with a combination of CZTS Alloysorbents 352, 353, and/or 354. Post-filter outlet manifold 392 routesthe non-gaseous emissions 295 to non-gaseous system discharge 256 bwhere some of the non-gaseous emissions 295 are expelled throughenvironmentally controlled non-gaseous release 273 and some of thenon-gaseous emissions 295 are expelled through a proper waste disposalstep 262. Additional post-filters can be added to post-filter inletmanifold 387, each filled with a different combination of CZTS Alloysorbents 352, 353, and/or 354, combined to effectively treat specificlevels and/or types of contaminates resident in non-gaseous emissions295.

All the pre-filters 381, 382, 383, 384 and post-filters 388, 389, 390,391 can be separately routed through sorbent cleaning step 258 andsorbent return port 260. Step 258 includes separating contaminates fromthe CZTS Alloy sorbents 351 so that the contaminates can be recycledand/or properly collected for disposal 261. Any exhausted CZTS Alloysorbents 351 can be disposed through disposal step 259. Replacement ofspecific CZTS Alloy sorbents 351 to each specific pre-filter 381, 382,383, 384 and/or post-filter 388, 389, 390, 391 may be implemented afterstep 258. Specific routing diagrams and/or schematics for routingsorbent from the pre-filters 388, 389, 390, 391 and/or post-filters 388,389, 390, 391 to and from the sorbent cleaning step 258 is not shown.

Referring to FIG. 33, an exemplary emission control system isillustrated. Contaminated emissions are introduced into fluidized bed152 via entry port 165. It should be appreciated that the emissions mayfirst pass through one or more pre-fluidized bed filters 151 (FIGS. 22and 23) depending on application specific requirements.

The fluidized bed 152 has a housing 16 with a reverse venturi shape,which has a specific length L to diameter D size ratio of between 2.9:1as a minimum and 9.8:1 as a maximum. This ratio is optimized forextended residence flow time of contaminated emissions in fluidized bed152, which is filled with specialized reactive material 164, whichincludes one or more sorbents. The preferred exemplary length L todiameter D ratio for fluidized bed 152 is 4.4:1, which has beendetermined through trial and error testing. One or more exemplaryfluidized beds 152 can be linked in series or in parallel as may berequired for application specific requirements.

Preferably, the fluidized bed 152 has a predominately round crosssection. While not shown in FIG. 33, one or more of the various bafflesand/or other application specific flow restriction obstacles disclosedherein can be incorporated into the fluidized bed 152. Fluidized bed 152also features predominately outward extending convex ends 168, 169 topromote extended residence flow time with minimized turbulent flowthrough reactive material 164. As the contaminated emissions flow entersfluidized bed 152 at entry port 165, intimate contact with reactivematerial 164 is initiated, resulting in random non-turbulent flow 166.Random non-turbulent flow 166 is turned back upon itself due to thepredominately outward extending convex ends 168, 169, resulting inextended residence time in fluidized bed 152 before the non-turbulentflow 166 exits from fluidized bed 152 through exit port 167. Reactivematerial 164 promotes random non-turbulent flow 166, which is arandomized torturous flow path for contaminated emissions. It should beappreciated that length L of the fluidized bed 152 is not inclusive ofthe convex ends 168, 169.

Fluidized bed 152 includes at least one monitoring sensor station 421(i.e., a first monitoring sensor) that provides data, status, andfeedback on the operating parameters. Monitoring sensor station(s) 421are equipped to monitor emission flow levels, pressure, velocity,temperature, and many other relevant parameters associated with theemissions control system. Based on feedback information, some automaticadjustments can be made by the equipment, while other process and/orsystem parameters may require manual adjustments. Monitoring sensorstations 421 provide information about the efficiency of the sorbentinside fluidized bed 152 and help determine when it is time to cleanand/or rejuvenate the sorbent.

In an exemplary embodiment of the subject disclosure, fluidized bed 152has at least one side outlet port 403, 409, 415 leading to sorbentrecycling subsystems 400, 401, 402 respectively. The sorbent recyclingsubsystems 400, 401, 402 shown in FIG. 33 are positioned external tofluidized bed 152, but alternatively, they can be installed insidefluidized bed 152.

Fluidized bed 152 includes at least one closed loop sorbent exit portmonitoring sensor station 422 and at least one closed loop sorbentreturn port monitoring sensor station 423 that provide data, status, andfeedback on the operating parameters. Monitoring sensor station 422 isconfigured to monitor emission flow levels, pressure, velocity,temperature, and many other relevant parameters associated with theemissions control system. Based on feedback information, some automaticadjustments can be made using programmable equipment, while otherprocess and/or system parameters may require manual adjustments.Monitoring sensor 423 identifies sorbent conditions as the sorbentpasses through one of the exit ports 403, 409, or 415 and into subsystem400, 401, or 402 respectively. Monitoring sensor station 423 isconfigured to monitor emission flow levels, pressure, velocity,temperature, and many other relevant parameters associated with theemissions control system.

Based on feedback information, some automatic adjustments can be madeusing programable equipment, while other process and/or systemparameters may require manual adjustments. Monitoring sensor 423identifies sorbent conditions as it passes through one of the returnports 407, 414, or 420 of subsystem 400, 401, or 402 respectively aftercleaning and/or rejuvenation. Monitoring sensor station 424 (i.e., asecond monitoring sensor) is configured to monitor emission flow levels,pressure, velocity, temperature, and many other relevant parametersassociated with the emissions control system. Based on feedbackinformation, some automatic adjustments can be made using programableequipment, while other process and/or system parameters may requiremanual adjustments. Monitoring sensor 424 monitors conditions andresulting volume of sorbent 164 as it is processed in station 404, 410,or 416 within subsystem 400, 401, or 402 respectively as the cleaningand/or rejuvenation process occurs. Monitoring sensors 421, 422, 423,424 are configured to cooperate with each other and provide processconditions and/or parameter adjustments to establish and maintainconsistency and optimum sorbent efficiency at each station in theemissions control system. Monitoring of sorbent within subsystems 400,401, 402 will determine when and how much makeup sorbent is requiredfrom station 408, 413, and 419 respectively.

In another exemplary embodiment (not shown), cleaning and/orrejuvenation subsystems are installed and configured internal tofluidized bed 152. In this configuration, the monitoring sensors 421,422, 423, 424 and functions of the sorbent recycling subsystems 400,401, 402 occur internal of the fluidized bed 152.

Still referring to FIG. 33, fluidized bed 152 will be filled withsorbent, which is CZTS, a CZTS-Alloy, a CZTS-Mixture, or somecombination of all three categorizations of sorbent. CZTS is a compoundwith four element ingredients (Copper, Zinc, Tin, Sulfur). Theseelements are pure chemical substances made of the same type of atom. ACZTS compound contains atoms of Copper, Zinc, Tin, and Sulfur that arechemically combined together in a fixed ratio to form a stable compound.Elements cannot be broken down into simpler substances by chemicalreactions. Compounds can be separated and/or broken down into simplersubstances by chemical methods and/or chemical reactions. Electrons ofatoms are shared between elements in the formation of compounds.

An alloy includes two or more chemical elements or compounds, of whichat least one is a metal. CZTS-Alloys include the four elements ofCopper, Zinc, Tin, and Sulfur, as well as at least one additionalelement or compound that is a metal, to form a CZTS-Alloy. The electronsof the at least one additional element or compound are shared with theCZTS compound to form a new compound in the form of an alloy.

CZTS-Mixtures include the CZTS compound combined with at least oneadditional element or compound. However, in contrast to CZTS-Alloys, theelectrons of CZTS compound and the at least one additional metallicelement or compound are not shared. The components of CZTS-Mixtures donot share the electrons of atoms. A common example of a mixture isdissolving a salt compound (NaCl) into a water compound (H₂O). Themixture will be a solution, but the atoms of salt and water will notshare any electrons between each other. Therefore, no new compound isformed, and the two compounds of salt and water are simply mixedtogether with no chemical bonding taking place.

When fluidized bed 152 is filled with reactive material 164 thatincludes CTZS sorbent, then sorbent recycling subsystem 400 is used tomaintain optimum process conditions for the CZTS sorbent. Sorbentdischarge port 403 allows transfer of sorbent into sorbent recyclingstation 404. The sorbent recycling station 404 in subsystem 400 includesone or more chemical reagents that separate contaminants from the CZTSsorbent as part of a cleaning and rejuvenation process. By way ofnon-limiting example, the chemical reagents used in the sorbentrecycling station 404 may be selected from a group of fatty alcohols.Spent and/or exhausted CZTS sorbent can be disposed of through sorbentdisposal station 405. Emission contaminants removed from emissions canbe recycled back into various industries through contaminant disposalport 406. Bulk refill station 408, such as a container of new/freshsorbent, provides a makeup supply of CZTS sorbent that replaces thesorbent that has been removed and/or lost during the removal ofcontaminants from emissions. CZTS sorbent return port 407 completes aclosed loop back into fluidized bed 152.

The cleaning and/or rejuvenation of CZTS can be accomplished usingsimple lipids, such as glycerin. Lipids containing phosphorous do notwork as well because the phosphorous is essentially a contaminateitself. Lipids with a low pH can lead to decomposition of the CZTS andevolve hydrogen sulfide (H₂S), leaving the sorbent Sulfur-deficient.Accordingly, additional rejuvenation steps are required to efficientlyuse low pH lipids. Testing has determined a minimum optimum pH range ofbetween 6.49-7.73 to avoid acidic degradation of CZTS. Testing hasfurther determined a maximum pH is limited to 9.05 to avoid basedegradation of CZTS. Glycolipids are preferred as their relativeviscosity is lower and therefore make it easier to maximize contact withthe sorbent and are easier to remove/separate from the sorbent after thecleaning and/or rejuvenation process is complete, especially when heatis applied. Glycolipids are also water soluble, so a dilute solution canbe used. Lipids with carbon atoms with a hydroxyl group are preferred asan optimum lipid for cleaning and/or rejuvenation of CZTS.

As an alternative to glycerin, some benefits for cleaning and/orrejuvenation of CZTS can be realized using long chain alcohols (cetyland stearyl alcohol) dissolved in hot water. However, glycerin ispreferred over all other known cleaning and/or rejuvenation substancesfor CZTS.

Captured contaminates such as mercury are soluble in simple lipids.Therefore, saturated CZTS with contaminates can be sprayed in thecleaning and/or rejuvenation station 404 to extract and separate thecontaminates from the CZTS. After separating the simple lipids with thesoluble contaminates from the CZTS, a steam rinse and/or hot water rinsecompletes the process of the rejuvenation of CZTS. The rinse can be apressurized rinse or a gravity flow rinse. This process completelycleans the CZTS of all contaminates and rejuvenates it to originalcondition so that it can be returned to fluidized bed 152 through returnport 407.

In accordance with this process, the simple lipids are heated to anoptimal temperature of between 85 degrees Celsius (° C.) and 110 degreesCelsius (° C.). The heated simple lipids are then sprayed on thesaturated CZTS. Based on contact time, a lower effective temperature forheating the simple lipids of 5 degrees Celsius (° C.) above ambient andan upper effective temperature of 140 degrees Celsius (° C.) will workfor the cleaning and/or rejuvenation of CZTS.

An alternative process to the use of simple lipids to separatecontaminates from CZTS, which can be integrated into the cleaning and/orrejuvenation station 404, is the use of a vacuum dryer because mercurycan be distilled and volatized. After contaminates are volatized in thevacuum dryer, the contaminates can be captured in filters and/orscrubbers. Scrubbers and filters can be especially effective whensaturated in diluted simple lipids.

Contaminated simple lipids, which have been separated from CZTS, can berecycled after discharge from contaminant disposal port 406 in a processwhere contaminates are separated from the simple lipids by normalindustry processes. After the separation of contaminates, the spentsimple lipids can be burned, while the contaminates are separatelycollected for recycling back into industry uses and/or proper disposal.If any CZTS has been lost due to handling during the cleaning and/orrejuvenation process, bulk refill station 408 restores CZTS to propervolumes in fluidized bed 152.

When fluidized bed 152 is filled with reactive material 164 thatincludes CTZS-Alloy sorbent, then sorbent recycling subsystem 401 isused to maintain optimum process conditions for the CZTS-Alloy sorbent.Sorbent discharge port 409 allows transfer of sorbent into sorbentrecycling station 410. The sorbent recycling station 410 in subsystem401 includes one or more chemical reagents that separate contaminantsfrom the CZTS-Alloy sorbent as part of a cleaning and rejuvenationprocess. By way of non-limiting example, the chemical reagents used inthe sorbent recycling station 410 may be selected from a group of fattyalcohols. Spent and/or exhausted CZTS-Alloy sorbent can be disposed ofthrough station 411. Emission contaminants removed from emissions can berecycled back into various industries through contaminant disposal port412. Bulk refill station 413 provides a makeup supply of CZTS-Alloysorbent that replaces the sorbent that has been removed and/or lostduring the removal of contaminants from emissions. CZTS-Alloy sorbentreturn port 414 completes a closed loop back into fluidized bed 152.

The cleaning and/or rejuvenation of CZTS-Alloy can be accomplished usingsimple lipids, such as glycerin. Lipids containing phosphorous do notwork as well because the phosphorous is essentially a contaminateitself. Lipids with a low pH can lead to decomposition of theCZTS-Alloys and evolve hydrogen sulfide (H₂S), leaving the sorbentSulfur-deficient. Accordingly, additional rejuvenation steps arerequired to efficiently use low pH lipids. Testing has determined aminimum optimum pH range of between 6.49-7.73 to avoid acidicdegradation of CZTS-Alloys. Testing has further determined a maximum pHis limited to 9.05 to avoid base degradation of CZTS-Alloys. Glycolipidsare preferred as their relative viscosity is lower and therefore make iteasier to maximize contact with the sorbent and are easier toremove/separate from the sorbent after the cleaning and/or rejuvenationprocess is complete, especially when heat is applied. Glycolipids arealso water soluble, so a dilute solution can be used. Lipids with carbonatoms with a hydroxyl group are preferred as an optimum lipid forcleaning and rejuvenation of CZTS-Alloys.

As an alternative to glycerin, some benefits for cleaning and/orrejuvenation of CZTS-Alloys can be realized using long chain alcohols(cetyl and stearyl alcohol) dissolved in hot water. However, glycerin ispreferred over all other known cleaning and/or rejuvenation substancesfor CZTS-Alloys.

Captured contaminates such as mercury are soluble in simple lipids.Therefore, saturated CZTS-Alloys with contaminates can be sprayed in thecleaning and/or rejuvenation station 410 to extract and separate thecontaminates from the CZTS-Alloys. After separating the simple lipidswith the soluble contaminates from the CZTS-Alloys, a steam rinse and/orhot water rinse completes the process of the rejuvenation ofCZTS-Alloys. The rinse can be a pressurized rinse or a gravity flowrinse. This process completely cleans the CZTS-Alloys of allcontaminates and rejuvenates it to original condition so that it can bereturned to fluidized bed 152 through return port 414.

In accordance with this process, the simple lipids are heated to anoptimal temperature of between 85 degrees Celsius (° C.) and 110 degreesCelsius (° C.). The heated simple lipids are then sprayed on thesaturated CZTS-Alloys. Based on contact time, a lower effectivetemperature for heating the simple lipids of 5 degrees Celsius (° C.)above ambient and an upper effective temperature of 140 degrees Celsius(° C.) will work for the cleaning and/or rejuvenation of CZTS-Alloys.

An alternative process to the use of simple lipids to separatecontaminates from CZTS-Alloys, which can be integrated into the cleaningand/or rejuvenation station 410, is the use of a vacuum dryer becausemercury can be distilled and volatized. After contaminates are volatizedin the vacuum dryer, the contaminates can be captured in filters and/orscrubbers. Scrubbers and filters can be especially effective whensaturated in diluted simple lipids.

Contaminated simple lipids, which have been separated from CZTS-Alloys,can be recycled after discharge from contaminant disposal port 412 in aprocess where contaminates are separated from the simple lipids bynormal industry processes. After separation of contaminates, the spentsimple lipids can be burned, while the contaminates are separatelycollected for recycling back into industry uses and/or proper disposal.If any CZTS-Alloy has been lost due to handling during the cleaningand/or rejuvenation process, bulk refill station 413 restores CZTS-Alloyto proper volumes in fluidized bed 152.

When fluidized bed 152 is filled with reactive material 164 thatincludes CZTS-Mixture sorbent, then sorbent recycling subsystem 402 isused to maintain optimum process conditions for the carbon-basedsorbent. Sorbent discharge port 415 allows transfer of sorbent intosorbent recycling station 416. The sorbent recycling station 416 insubsystem 402 includes one or more chemical reagents that separatecontaminants from the carbon-based sorbent as part of a cleaning andrejuvenation process. By way of non-limiting example, the chemicalreagents used in the sorbent recycling station 416 may be solvents suchas Methyl Ethyl Ketone, Methylene Chloride, and/or Methanol. Spentand/or exhausted carbon-based sorbent can be disposed of through sorbentdisposal station 417. Emission contaminants removed from emissions canbe recycled back into various industries through contaminant disposalport 418. Bulk refill station 419 provides a makeup supply ofcarbon-based sorbent that replaces the sorbent that has been removedand/or lost during the removal of contaminants from emissions.Carbon-based sorbent return port 420 completes a closed loop back intofluidized bed 152.

The cleaning and/or rejuvenation of CZTS-Mixture can be accomplishedusing simple lipids, such as glycerin. Lipids containing phosphorous donot work as well because the phosphorous is essentially a contaminateitself. Lipids with a low pH can lead to decomposition of theCZTS-Mixture and evolve hydrogen sulfide (H₂S), leaving the sorbentSulfur-deficient. Accordingly, additional rejuvenation steps arerequired to efficiently use low pH lipids. Testing has determined aminimum optimum pH range of between 6.49-7.73 to avoid acidicdegradation of CZTS-Mixtures. Testing has further determined a maximumpH is limited to 9.05 to avoid base degradation of CZTS-Mixtures.Glycolipids are preferred as their relative viscosity is lower andtherefore make it easier to maximize contact with the sorbent and areeasier to remove/separate from the sorbent after the cleaning and/orrejuvenation process is complete, especially when heat is applied.Glycolipids are also water soluble, so a dilute solution can be used.Lipids with carbon atoms with a hydroxyl group are preferred as anoptimum lipid for cleaning and rejuvenation of CZTS-Mixture.CZTS-Mixtures include, but are not limited to, coating granulated ferricoxide with CZTS or coating carbon-based sorbents with CZTS.

As an alternative to glycerin, some benefits for cleaning and/orrejuvenation of CZTS-Mixture can be realized using long chain alcohols(cetyl and stearyl alcohol) dissolved in hot water. However, glycerin ispreferred over all other known cleaning and/or rejuvenation substancesfor CZTS-Mixture.

Captured contaminates such as mercury are soluble in simple lipids.Therefore, saturated CZTS-Mixture with contaminates can be sprayed inthe cleaning and/or rejuvenation station 416 to extract and separate thecontaminates from the CZTS-Mixture. After separating the simple lipidswith the soluble contaminates from the CZTS-Mixture, a steam rinseand/or hot water rinse completes the process of the rejuvenation ofCZTS-Mixture. The rinse can be pressurized rinse or a gravity flowrinse. This process completely cleans the CZTS-Mixture of allcontaminates and rejuvenates it to original condition so that it can bereturned to fluidized bed 152 through return port 420.

In accordance with this process, the simple lipids are heated to anoptimal temperature of between 85 degrees Celsius (° C.) and 110 degreesCelsius (° C.). The heated simple lipids are then sprayed on thesaturated CZTS-Mixture. Based on contact time, a lower effectivetemperature for heating the simple lipids of 5 degrees Celsius (° C.)above ambient and an upper effective temperature of 140 degrees Celsius(° C.) will work for the cleaning and/or rejuvenation of CZTS-Mixture.

An alternative process to the use of simple lipids to separatecontaminates from CZTS-Mixture, which can be integrated into thecleaning and/or rejuvenation station 416, is the use of a vacuum dryerbecause mercury can be distilled and volatized. After contaminates arevolatized in the vacuum dryer, the contaminates can be captured infilters and/or scrubbers. Scrubbers and filters can be especiallyeffective when saturated in diluted simple lipids. Granulated ferricoxide coated with CZTS as a mixture is particularly efficient to extractphosphates from contaminated emissions and will volatize in a vacuumdryer.

Contaminated simple lipids which have been separated from CZTS-Mixturecan be recycled after discharge from contaminant disposal port 418 in aprocess where contaminates are separated from the simple lipids bynormal industry processes. After separation of contaminates, the spentsimple lipids can be burned, while the contaminates are separatelycollected for recycling back into industry uses and/or proper disposal.If any CZTS-Mixture has been lost due to handling during the cleaningand/or rejuvenation process, bulk refill station 419 restoresCZTS-Mixture to proper volumes in fluidized bed 152.

According to one exemplary embodiment of the subject disclosure, and asshown in FIG. 33, fluidized bed 152 can be a single unit with one ormore sorbent recycling subsystems 400, 401, 402 configured for one ormore sorbents. According to another exemplary embodiment (not shown),multiple fluidized beds 152 can be configured in series with each other,where each fluidized bed 152 is configured for one or more sorbentrecycling subsystems 400, 401, 402. According to another exemplaryembodiment (not shown), multiple fluidized beds 152 can be configured inparallel with each other, where each fluidized bed 152 is configured forone or more sorbent recycling subsystems 400, 401, 402.

Monitoring sensors 421, 422, 423, 424 are just a few non-exhaustiveexamples of measuring equipment that can be applied to the emissionscontrol system. Those skilled in the art will appreciate that there maybe many additional types of monitoring sensors located in many otherstations of the emissions control system which have not been shown inthe illustrated embodiments. The specific monitoring sensors used forgaseous contaminated emissions may be different than the specificmonitoring sensors used for non-gaseous contaminated emissions.Similarly, the monitoring sensors required for one type of contaminantmay be different than the monitoring sensors required for anothercontaminant.

In accordance with another aspect of the subject disclosure, anemissions control method is disclosed for removing contaminants fromemissions. The method, which is illustrated in FIG. 33, includes thesteps of routing the emissions into a treatment system including areverse venturi shaped fluidized bed apparatus 152 containing one ormore sorbents that chemically binds with contaminants carried in theemissions and routing the emissions away from the reverse venturi shapedfluidized bed apparatus 152 after the contaminants bind to the sorbents.In accordance with this method, the sorbent(s) is/are selected from agroup of materials including: copper, zinc, tin, sulfur (CZTS) sorbents,copper, zinc, tin, sulfur (CZTS) alloy sorbents, and CZTS-Mixturesorbents. The method also includes the step of routing the sorbentthrough one or more sorbent recycling subsystems 400, 401, 402 forcleaning and rejuvenation. This step includes separating spent andexhausted sorbent from the sorbent routed through the sorbent recyclingsubsystem(s) 400, 401, 402, disposing of the spent and exhaust sorbent,separating contaminants from the sorbent routed through the sorbentrecycling subsystem(s) 400, 401, 402, disposing of or recycling thecontaminants, and returning the recycled sorbent to the reverse venturishaped fluidized bed apparatus 152. Optionally, the method may includethe step of routing new sorbent to the reverse venturi shaped fluidizedbed apparatus 152 to replace the spent and exhaust sorbent.

In embodiments where the reverse venturi shaped fluidized bed apparatus152 includes multiple sorbent recycling subsystems 400, 401, 402, themethod may further include the steps of: maintaining different sorbentsseparate from one another in the reverse venturi shaped fluidized bedapparatus 152, detecting at least one process parameter of the reverseventuri shaped fluidized bed apparatus with one or more monitoringsensors 421, 422, 423, 424, routing the emissions through one or more ofthe different sorbents based on the at least one process parameterdetected by the monitoring sensor(s) 421, 422, 423, 424, and thenrouting the different sorbents through different sorbent recyclingsubsystems 400, 401, 402 that are dedicated to processing a particulartype of sorbent. For example, in the illustrated embodiment, copper,zinc, tin, sulfur (CZTS) sorbents are routed through first sorbentrecycling subsystem 400, copper, zinc, tin, sulfur (CZTS) alloy sorbentsare routed through second sorbent recycling subsystem 401, and copper,zinc, tin, sulfur (CZTS)-Mixture sorbents are routed through thirdsorbent recycling subsystem 402.

Extraction of Target Materials Using CZTS Sorbent.

Various embodiments of the present invention provide a method ofextracting a target material from a medium. The method can includecontacting a copper zinc tin sulfur (CZTS) sorbent with the targetmaterial in the medium including the target material. The contactingforms a used CZTS sorbent that includes the target material. Prior tothe contacting, the CZTS sorbent can be substantially free of the targetmaterial or can include some target material. The used CZTS sorbentincludes more of the target material than the CZTS sorbent prior to thecontacting. The method also includes separating the used CZTS sorbentfrom the medium. In some embodiments, the method also includes removingthe target material from the used CZTS sorbent, to obtain an extractincluding the target material.

The method can include contacting the CZTS sorbent with the targetmaterial in any apparatus, such as the reverse venturi apparatusdescribed herein, or such as any other suitable apparatus. The targetmaterial can be any suitable target material that can be at leastpartially removed from a medium with the CZTS sorbent using the methoddescribed herein, including but not limited to any material described asa contaminant herein.

Target Material.

The target material can be any suitable target material. The method canremove one target material from the medium or more than one targetmaterial. The target material can include a gas, a liquid, a solid, asolute, or a combination thereof. The target material can include anymaterial described herein as a contaminant, a metal, a heavy metal, aprecious metal, a rare earth metal, sulfur, nitrogen, nitrogen dioxide,a nitrate, phosphorus, a phosphate, sulfur, sulfur dioxide, ammonia,boron, a compound thereof, a complex thereof, a salt thereof, an organicsolvent (e.g., a volatile organic solvent, such as benzene), or acombination thereof.

The target material can include a precious metal. The target materialcan include a coinage group metal, a platinum group metal, or acombination thereof. The target material can include gold, silver, acompound thereof, a complex thereof, a salt thereof, an oxide thereof,or a combination thereof. The target material can include gold, silver,or a combination thereof. The target material can include ruthenium,rhodium, palladium, osmium, iridium, platinum, a compound thereof, acomplex thereof, a salt thereof, an oxide thereof, or a combinationthereof. The target material can include ruthenium, rhodium, palladium,osmium, iridium, platinum, or a combination thereof.

The target material can include a rare earth metal. The target materialcan include cerium, dysprosium, erbium, europium, gadolinium, holmium,lanthanum, lutetium, neodymium, praseodymium, promethium, samarium,scandium, terbium, ytterbium, yttrium, a compound thereof, a complexthereof, a salt thereof, an oxide thereof, or a combination thereof. Thetarget material can include cerium, dysprosium, erbium, europium,gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium,promethium, samarium, scandium, terbium, ytterbium, yttrium, or acombination thereof.

The target material can include a polluting substance, a toxicsubstance, a poisonous substance, or a combination thereof. The targetmaterial can include mercury, arsenic, barium, beryllium, cadmium,chromium, copper, lead, molybdenum, nickel, radium, selenium, aselenate, thorium, uranium, vanadium, zinc, tin, a compound thereof, acomplex thereof, a salt thereof, an oxide thereof, or a combinationthereof. The target material can include mercury, an oxide thereof, or acombination thereof.

CZTS Sorbent.

The CZTS sorbent includes the elements copper, zinc, tin, and sulfur,which can be present in elemental form (e.g., as a mixture with oneanother), as one or more compounds including two or more of the elements(copper, zinc, tin, and sulfur), or a combination thereof. The CZTSsorbent can optionally include other elements, compounds thereof (e.g.,compounds including only the other elements or also including copper,zinc, tin, and sulfur), or combinations thereof. The copper, zinc, tin,and sulfur can form the bulk or the CZTS sorbent, or can be present as acoating on another material to increase the surface area of combinationof the copper, zinc, tin, and sulfur. Together the copper, zinc, tin,and sulfur can form any suitable proportion of the CZTS sorbent, such as0.001 wt % to 100 wt % of the CZTS sorbent, 50 wt % to 100 wt %, or0.001 wt % or more, or less than, equal to, or greater than 0.005 wt %,0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25,30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92,93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt % orless.

In some embodiments, the CZTS sorbent includes copper zinc tin sulfidehaving the formula Cu₂ZnSnS₄. Cu₂ZnSnS₄ is a I₂-II-IV-VI₄ quaternarycompound that can have semiconducting properties. Cu₂ZnSnS₄ can have akesterite structure. The Cu₂ZnSnS₄ can be present as an alloy, in anunalloyed form, or a combination thereof. The Cu₂ZnSnS₄ can form anysuitable proportion of the CZTS sorbent, such as 0.001 wt % to 100 wt %of the CZTS sorbent, 50 wt % to 100 wt %, or 0.001 wt % or more, or lessthan, equal to, or greater than 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2,3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99,99.9, 99.99, or 99.999 wt %, or 100 wt % or less.

In some embodiments, the CZTS sorbent includes ZnS, CuS, Cu₂SnS₃, CuZn₂,SnS, or a combination thereof; in other embodiments, the CZTS sorbent issubstantially free of ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combinationthereof. The ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or combination can be one ormore phases within the CZTS, as a mixture within the CZTS, or acombination thereof. The ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or combinationthereof can be present with Cu₂ZnSnS₄, or the CZTS sorbent can besubstantially free of Cu₂ZnSnS₄. The ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, orcombination thereof can be any suitable proportion of the CZTS sorbent,such as 0.001 wt % to 100 wt % of the CZTS sorbent, 50 wt % to 100 wt %,or 0.001 wt % or more, or less than, equal to, or greater than 0.005 wt%, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91,92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt %or less.

The CZTS sorbent can be substantially free of an element, metal, orcompound in addition to copper, zinc, tin, and sulfur; in otherembodiments, the CZTS sorbent can include an element, metal, or compoundin addition to copper, zinc, tin, and sulfur. The element, metal, orcompound in the CZTS sorbent can be included in the CZTS sorbent as amixture, as an alloy, as a coating thereon, as a CZTS-coated material(e.g., such that coating of CZTS on the material increases the surfacearea of the material and uses the CZTS more efficiently in the method),or a combination thereof. The element, metal, or compound can includezinc, iron, aluminum, sulfur, selenium, a selenite, ferrous oxide,ferric oxide, or a combination thereof. The element, metal, or compoundcan include a clay, zeolite, a hydroxide salt, or a combination thereof.The element, metal, or compound can include bentonite, zeolite, calciumhydroxide, or a combination thereof. The element, metal, compound, orcombination thereof can form any suitable proportion of the CZTSsorbent, such as 0.001 wt % to 99.999 wt % of the CZTS sorbent, 0.001 wt% to 70 wt %, 0.001 wt % to 20 wt %, or 0.001 wt % or more, or lessthan, equal to, or greater than 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2,3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99,99.9, or 99.99 wt %, or 99.999 wt % or less.

The CZTS sorbent can have any suitable one or more physical forms whenused for the removal of the target material from the medium. The CZTSsorbent can include particulate CZTS, monolithic CZTS, a CZTS coating, aCTZS sheet, a CTZS film, or a combination thereof.

The CZTS sorbent can have any suitable particle size, such as avolume-average particle size (e.g., 10%, 50%, 90%, or 100%volume-average particle size) of 0.5 nm to 3 inches, 0.5 nm to 7,500microns, 0.5 nm or more, less than, equal to, or greater than 1 nm, 2,3, 4, 5, 6, 8, 10, 15, 20, 25, 50, 100, 150, 200, 250, 400, 600, 800 nm,1 micron, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 85, 90, 95, 100, 150, 200, 250, 400, 600, 800 microns, 1mm, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,70, or 75 mm, or 3 inches or less. The CZTS sorbent can have a 10%volume-average particle size of 0.01 microns to 1 micron, or 0.1 micronto 0.3 microns. The CZTS sorbent can have a 50% volume-average particlesize of 1 micron to 20 microns, or 5 microns to 15 microns. The CZTSsorbent can have a 90% volume-average particle size of 10 microns to 40microns, or 20 microns to 30 microns. The CZTS sorbent can have a 100%volume-average particle size of 20 microns to 60 microns, or 30 micronsto 50 microns.

The CZTS sorbent can have any suitable surface area. The CZTS can have asurface area of 0.2 m²/g to 2000 m²/g, 1 m²/g to 30 m²/g, 10 m²/g to 15m²/g, or 0.2 m²/g or more, or less than, equal to, or greater than 0.4m²/g, 0.6, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 60, 70, 80, 90,100, 150, 200, 500, 750, 1,000, 1,250, 1,500, 1,750 m²/g, or 2,000 m²/gor less.

The CZTS sorbent can have any suitable density. The CZTS sorbent canhave a density of 2 to 8 g/cm³, or 4 to 5 g/cm³, or 4.5 to 4.6 g/cm³, or2 g/cm³ or more, or less than, equal to, or greater than 2.2 g/cm³, 2.4,2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4,5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, or 7.8 g/cm³, or 8.0g/cm³ or less.

Contacting the CZTS Sorbent with the Target Material.

The method includes contacting the CZTS sorbent with the target materialin the medium including the target material. The method can includecontacting the CZTS sorbent with the target material in any apparatus,such as the reverse venturi apparatus described herein, or such as anyother suitable apparatus that provides removal of the target materialfrom the medium by the sorbent. The contacting can include contactingthe CZTS sorbent and the medium, such that the target material in themedium contacts the CZTS sorbent. The contacting of the CZTS sorbent andthe target material can include flowing the medium through a fixed bedincluding the CZTS sorbent, flowing the medium through a columnincluding the CZTS sorbent, flowing the medium through an apparatusincluding the CZTS sorbent deposited therein, suspending the CZTSsorbent in the medium, injecting the CZTS sorbent into the medium, or acombination thereof. In some embodiments, the contacting includesflowing the medium through a reverse-venturi apparatus including theCZTS sorbent deposited therein.

The contacting can be performed at any suitable temperature. Thecontacting can be performed at ambient temperature. The contacting canbe performed at a temperature of −100° C. to 5,000° C., 1° C. to 300°C., or −100° C. or more, or less than, equal to, or greater than −90°C., −80, −70, −60, −50, −40, −30, −20, −10, −5, 0, 5, 10, 15, 20, 25,30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110,115, 120, 125, 130, 140, 150, 175, 200, 250, 500, 1,000, 1,500, 2,000,or 2,500° C., or 5,000° C. or less.

The contacting can be performed for any suitable duration. Thecontacting can including a continuous process, such as including flowingthe medium including the target material by the CZTS sorbent at anysuitable flow rate. The contacting can include a batch-type process,such as allowing the medium including the target material to sit incontact with the CZTS sorbent for a suitable period of time. Thecontacting can be performed with or without agitation of the medium toensure adequate and effective contact with the CZTS sorbent. Thecontacting between the CZTS sorbent and the target material in themedium can be performed for a duration of 30 d to 0.000001 s, 1 h to0.000001 s, or 30 d or less, or less than, equal to, or greater than 25d, 20, 15, 10, 5, 1 d, 20 h, 16, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1h, 50 min, 40, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1 min, 50 s, 40, 30, 25,20, 15, 10, 5, 4, 3, 2, 1 s, 0.1, 0.01, 0.001, 0.0001, or 0.00001 s, or0.000001 s or more.

The medium can be any suitable material that includes the targetmaterial. The medium can include a liquid, gas, or a combinationthereof. The medium can include water, an organic solvent, an oil, or acombination thereof. The medium can be an aqueous medium or an organicmedium. The aqueous medium can include any suitable proportion of water,such as 50 wt % to 100 wt % of the aqueous medium, 80 wt % to 100 wt %,50 wt % or more, or less than, equal to, or greater than 55, 60, 65, 70,75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, 99.999wt %, or 100 wt/o or less.

The medium can include liquid or gaseous effluent from a combustionprocess, such as from a power plant, such as from a coal-firedelectrical plant. The medium can include flue gas from a coal-firedelectrical plant, water from the coal-fired electrical plant (e.g., usedfor scrubbing the flue gas), or a combination thereof.

The medium can include a medium used in or obtain from a miningoperation. The medium from a mining operation in some examples can be anaqueous medium. In some embodiments, the mining operation is a miningoperation to mine the target material; in other embodiments, another oneor more materials other than the target material is the objective of themining operation and removal of the target material is ancillary to theprimary target of the mining operation (e.g., wherein the primary targetcan refer to the largest volume target, the target that generates thegreatest profit, or a combination thereof).

The target material can form any suitable proportion of the medium. Thetarget material can be 1 part per trillion to 99.999 wt % of the medium,0.001 wt % to 20 wt % of the medium, or 1 part per trillion or more, 10parts per trillion, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 partsper trillion, 1 part per billion, 10 parts per billion, 20, 25, 50, 75,100, 150, 200, 250, 500, 750 parts per billion, 1 part per million, 10parts per million, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 partsper million, 0.001 wt %, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35,40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97,98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt % or less.

Used CZTS Sorbent.

The used CZTS sorbent includes the target material. The used CZTSsorbent includes a greater concentration of the target material than theCZTS prior to contacting with the target material, wherein the CZTSprior to contacting the target material can either include some targetmaterial or can be substantially free of the target material. The usedCZTS sorbent can include the target material in any suitable form on orin the used CZTS sorbent such as absorbed on and/or in the CZTS sorbent,adsorbed and/or in the CZTS sorbent, complexed on and/or in the CZTSsorbent, amalgamed on and/or in the CZTS sorbent, or a combinationthereof. The used CZTS sorbent can include the target material in anunchanged chemical state as compared to the form of the target materialin the medium, as a complex, compound, or amalgam formed with the CZTSsorbent (e.g., as an amalgam with materials in the CZTS sorbent, such aswith Cu₂ZnSnS₄, ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combinationthereof), or a combination thereof.

The target material can be any suitable proportion of the used CZTSsorbent. The target material can be 1 part per trillion to 50 wt % ofthe used CZTS sorbent, 0.0001 wt % to 20 wt %, or 1 part per trillion ormore, 10 parts per trillion, 20, 25, 50, 75, 100, 150, 200, 250, 500,750 parts per trillion, 1 part per billion, 10 parts per billion, 20,25, 50, 75, 100, 150, 200, 250, 500, 750 parts per billion, 1 part permillion, 10 parts per million, 20, 25, 50, 75, 100, 150, 200, 250, 500,750 parts per million, 0.001 wt %, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25,30, 35, 40, or 45 wt %, or 50 wt % or less.

Separating the Used CZTS Sorbent from the Medium.

The method can include separating the used CZTS sorbent from the medium.The separating can be performed in any suitable way that removes theused CZTS sorbent from the bulk of the medium. The separating caninclude removing the used CZTS sorbent from the medium, removing themedium from the used CZTS sorbent, or a combination thereof.

The removal of the used CZTS sorbent from the medium can occur byflowing the medium by the CZTS sorbent, such that the medium previouslycontacted with the CZTS sorbent has flowed by the CZTS sorbent such thatthe used CZTS sorbent is no longer in contact with the medium previouslycontacted with the CZTS sorbent. As such, the removal can occurnaturally as a property of the contacting process; for example, theremoving can include flowing the medium through a fixed bed includingthe CZTS sorbent, flowing the medium through a column including the CZTSsorbent, flowing the medium through an apparatus including the CZTSsorbent deposited therein, or a combination thereof. The removing caninclude removing the medium from a suspension of the CZTS sorbent in themedium. The removing can include removing CZTS sorbent from a mediuminto which the CZTS sorbent was placed or injected. The separating caninclude separating the used CZTS sorbent from the medium using aparticulate separation device, such as a filter, an electrostaticprecipitator, a scrubber, or a combination thereof. The separating caninclude filtering the used CZTS sorbent from the medium. In someembodiments, the separating can include replacing the medium includingthe target material with a different medium, such as another mediumincluding the target material, a medium including less of the targetmaterial, or a medium that is substantially free of the target material.The separating can include rinsing the used CZTS sorbent, such as withan organic medium, an aqueous medium, or a combination thereof.

Any suitable proportion of the medium that is separated from the usedCZTS sorbent can be the target material. The medium that is separatedfrom the used CZTS sorbent can have a lower concentration of the targetmaterial than the medium including the target material prior tocontacting with the CZTS sorbent. The target material can be 0 wt % to99.99 wt % of the medium having the CZTS sorbent separated therefrom, 0wt % to 20 wt %, 0 wt % to 5 wt %, 0 wt % to 0.1 wt %, or 0 wt % ormore, or less than, equal to, or greater than 0.01, 0.02, 0.04, 0.06,0.08, 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.5, 3, 3.5, 4,4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, 99.9 wt %, or 99.99 wt % or less. In someembodiments, the medium having the CZTS sorbent separated therefrom issubstantially free of the target material.

Removing the Target Material from the Used CZTS Sorbent, to Obtain anExtract Including the Target Material.

In various embodiments, the method can include removing the targetmaterial from the used CZTS sorbent. Removal of the target material fromthe used CZTS sorbent provides an extract that includes the targetmaterial. The extract can be enriched in the target material relative tothe medium that included the target material prior to contacting withthe CZTS sorbent. The extract can include a greater concentration of thetarget material than a concentration of the target material in themedium prior to contacting with the CZTS sorbent. The target materialcan be any suitable proportion of the extract, such as 1 part pertrillion to 100 wt % of the extract, 0.001 wt % to 99.9 wt % of theextract, or 1 part per trillion or more, 10 parts per trillion, 20, 25,50, 75, 100, 150, 200, 250, 500, 750 parts per trillion, 1 part perbillion, 10 parts per billion, 20, 25, 50, 75, 100, 150, 200, 250, 500,750 parts per billion, 1 part per million, 10 parts per million, 20, 25,50, 75, 100, 150, 200, 250, 500, 750 parts per million, 0.001 wt %,0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9,99.99, or 99.999 wt %, or 100 wt % or less.

The extract can include a liquid or gas used for the removing of thetarget material from the used CTZS sorbent, a derivative of a liquid orgas used for the removing of the target material from the used CTZSsorbent, or a combination thereof. The extract can be substantially freeof the CZTS sorbent, or can include some CZTS sorbent (e.g., less of theCZTS sorbent than was present in the used CZTS sorbent). The extract canbe substantially free of Cu₂ZnSnS₄, ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or acombination thereof, or the extract can include one or more of thesematerials. The extract can be substantially free of the medium, or theextract can include some of the medium.

The removing of the target material from the medium can be performed inany suitable way that generates the extract. The removing can includeheating the used CZTS sorbent, extracting the target material from theused CZTS sorbent using liquid or gaseous extraction, dissolving theCZTS from the used CZTS sorbent (e.g., via reaction with one or moreacids or other materials), chemically-reacting the target material inthe CZTS sorbent, chemically-reacting the CZTS in the used CZTS sorbent,or a combination thereof. The removing can include placing the used CZTSsorbent in a vacuum drier. The removing can include rinsing the usedCZTS sorbent with an aqueous medium, an organic medium, or a combinationthereof. The removing can include rinsing the used CZTS sorbent withwater or steam.

The removing can include contacting the used CZTS sorbent with achemical reagent including an organic solvent, a fatty alcohol, a lipid,a glycolipid, or a combination thereof, optionally as a mixture withwater. The chemical reagent can include methanol, methyl ethyl ketone,methylene chlorine, glycerin, cetyl alcohol, stearyl alcohol, or acombination thereof, optionally as a mixture with water. The contactingof the used CZTS sorbent with the chemical reagent can be conductedunder any suitable pH conditions, such as at a pH of 1 to 20, 6.49 to9.05, or 1 or more, or less than, equal to, or greater than 2, 3, 4, 5,5.5, 6, 6.1, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, 8, 8.2, 8.4,8.6, 8.8, 9, 9.2, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19, or 20or less. The contacting of the used CZTS sorbent with the chemicalreagent can be performed at any suitable temperature, such as 5 to 140°C., 85 to 110° C., or 5° C. or more, or 10° C., 15, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120,125, 130, 135° C., or 140° C. or less.

The removal of the target material from the used CZTS sorbent canprovide a recovered CTZS sorbent. In some embodiments, the recoveredCTZS sorbent can be disposed of or otherwise used without reuse in themethod of extracting target materials with the CTZS sorbent. In someembodiments, the method includes reusing the recovered CTZS sorbent oneor more times in the method. The method can include processing therecovered CZTS sorbent such that the recovered CZTS sorbent is effectivefor reuse in the method as the CTZS sorbent; in some embodiments,removing the target material from the used CZTS is the only processingneeded to prepare the sorbent for reuse, while in other embodimentsfurther processing steps are included to prepare the recovered CZTSsorbent for reuse.

Method of Forming a CZTS Sorbent.

In various embodiments, the present invention provides a method offorming the CTZS sorbent describes herein. The method can includecombining copper, zinc, tin, and sulfur starting materials, in theirelemental form, as compounds (e.g., compounds of one another, includingother materials, or a combination thereof), as salts (e.g., salts of oneanother, including other materials, or a combination thereof), or acombination thereof, under conditions suitable to provide the CTZSsorbent. The method can include mixing the starting materials, such asbefore heating, during heating, or a combination thereof.

In some embodiments, the method includes combining a copper salt (e.g.,copper acetate dihydrate), a zinc salt (e.g., zinc acetate dihydrate), atin salt (e.g., tin chloride dihydrate), and a sulfur compound (e.g.,thiourea) in proportions suitable for and under conditions suitable forforming the CTZS sorbent.

The copper, zinc, tin, and sulfur in the mixture of starting materialcan independently form any suitable proportion of the starting materialmixture, such that a CTZS sorbent that can be used in the method ofextraction of target materials is formed. The copper in the mixture ofstarting materials can be 20 wt % to 30 wt %, 24 wt % to 26 wt %, 24.5wt % to 25.5 wt %, or about 24.92 wt % of the total copper, zinc, tin,and sulfur present in the starting material mixture. The zinc in themixture of starting materials can be 10 wt % to 25 wt %, 15 wt/o to 20wt %, 17 wt % to 19 wt %, 17.5 wt % to 18.5 wt %, or about 18.10 wt % ofthe total copper, zinc, tin, and sulfur present in the starting materialmixture. The tin in the mixture of starting materials can be 20 wt % to35 wt %, 25 wt % to 30 wt %, 26 wt % to 28 wt %, 26.5 wt % to 28 wt %,or about 27.39 wt % of the total copper, zinc, tin, and sulfur presentin the starting material mixture. The sulfur in the mixture of startingmaterials can be 25 wt %/o to 30 wt %, 28 wt % to 32 wt %, 29 wt % to 30wt %, or about 29.59 wt % of the total copper, zinc, tin, and sulfurpresent in the starting material mixture.

The method can include heating the starting materials. The heating canbe performed for any suitable duration, such as 1 min to 24 h, 20 min to4 h, or 1 min or more, or less than, equal to, or greater than 2 min, 4,6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 min, 1 h, 1.5, 2, 2.5, 3,3.5, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22 h, or 24 h or less. Theheating can include heating to any suitable temperature, such as 50° C.to 1,000° C., 75° C. to 300° C., or 50° C. or more, or less than, equalto, or greater than 60° C., 70, 80, 90, 100, 110, 120, 140, 160, 180,200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 500, 600, 700,800, or 900° C., or 1,000° C. or less. The method can include grindingor otherwise physically processing the reaction product to provide CTZSsorbent having the desired particle size.

The method of forming the CZTS sorbent can include adding one or moreadditional materials to the copper, zinc, tin, and sulfur startingmaterials. The method can include adding water to the starting materialsprior to the heating, during the heating, or a combination thereof.

It should be appreciated that although the steps of the methods aredescribed and illustrated herein in a particular order, the steps may beperformed in a different order without departing from the scope of thesubject disclosure, except where the order of the steps is otherwisenoted. In the same vein, it should be appreciated that the methodsdescribed and illustrated herein may be performed without the inclusionof all the steps described above or with the addition of interveningsteps that have not been discussed, all without departing from the scopeof the subject disclosure.

Many modifications and variations of the present disclosure are possiblein light of the above teachings and may be practiced otherwise than asspecifically described while within the scope of the appended claims.

Exemplary Embodiments

The following exemplary embodiments are provided, the numbering of whichis not to be construed as designating levels of importance:

Embodiment 1 provides a method of extracting a target material from amedium, the method comprising:

-   -   contacting a copper zinc tin sulfur (CZTS) sorbent with the        target material in the medium comprising the target material to        form a used CZTS sorbent that comprises the target material; and    -   separating the used CZTS sorbent from the medium.

Embodiment 2 provides the method of Embodiment 1, further comprisingremoving the target material from the used CZTS sorbent, to obtain anextract comprising the target material.

Embodiment 3 provides the method of any one of Embodiments 1-2, whereinthe target material comprises a metal, a heavy metal, a precious metal,a rare earth metal, sulfur, nitrogen, nitrogen dioxide, a nitrate,phosphorus, a phosphate, sulfur, sulfur dioxide, ammonia, boron, acompound thereof, a complex thereof, a salt thereof, an organic solvent,or a combination thereof.

Embodiment 4 provides the method of any one of Embodiments 1-3, whereinthe target material comprises a precious metal.

Embodiment 5 provides the method of any one of Embodiments 1-4, whereinthe target material comprises a coinage group metal, a platinum groupmetal, or a combination thereof.

Embodiment 6 provides the method of any one of Embodiments 1-5, whereinthe target material comprises gold, silver, a compound thereof, acomplex thereof, a salt thereof, an oxide thereof, or a combinationthereof.

Embodiment 7 provides the method of any one of Embodiments 1-6, whereinthe target material comprises gold, silver, or a combination thereof.

Embodiment 8 provides the method of any one of Embodiments 1-7, whereinthe target material comprises ruthenium, rhodium, palladium, osmium,iridium, platinum, a compound thereof, a complex thereof, a saltthereof, an oxide thereof, or a combination thereof.

Embodiment 9 provides the method of any one of Embodiments 1-8, whereinthe target material comprises ruthenium, rhodium, palladium, osmium,iridium, platinum, or a combination thereof.

Embodiment 10 provides the method of any one of Embodiments 1-9, whereinthe target material comprises a rare earth metal.

Embodiment 11 provides the method of any one of Embodiments 1-10,wherein the target material comprises cerium, dysprosium, erbium,europium, gadolinium, holmium, lanthanum, lutetium, neodymium,praseodymium, promethium, samarium, scandium, terbium, ytterbium,yttrium, a compound thereof, a complex thereof, a salt thereof, an oxidethereof, or a combination thereof.

Embodiment 12 provides the method of any one of Embodiments 1-11,wherein the target material comprises cerium, dysprosium, erbium,europium, gadolinium, holmium, lanthanum, lutetium, neodymium,praseodymium, promethium, samarium, scandium, terbium, ytterbium,yttrium, or a combination thereof.

Embodiment 13 provides the method of any one of Embodiments 1-12,wherein the target material comprises a polluting substance, a toxicsubstance, a poisonous substance, or a combination thereof.

Embodiment 14 provides the method of any one of Embodiments 1-13,wherein the target material is mercury, arsenic, barium, beryllium,cadmium, chromium, copper, lead, molybdenum, nickel, radium, selenium,selenates, thorium, uranium, vanadium, zinc, tin, a compound thereof, acomplex thereof, a salt thereof, an oxide thereof, or a combinationthereof.

Embodiment 15 provides the method of any one of Embodiments 1-14,wherein the target material is mercury, an oxide thereof, or acombination thereof.

Embodiment 16 provides the method of any one of Embodiments 1-15,wherein the target material is a gas, a liquid, a solid, a solute, or acombination thereof.

Embodiment 17 provides the method of any one of Embodiments 1-16,wherein the target material is 1 part per trillion to 99.999 wt % of themedium.

Embodiment 18 provides the method of any one of Embodiments 1-17,wherein the target material is 0.001 wt % to 20 wt % of the medium.

Embodiment 19 provides the method of any one of Embodiments 1-18,wherein the medium comprises liquid, gas, or a combination thereof.

Embodiment 20 provides the method of any one of Embodiments 1-19,wherein the medium comprises water, an organic solvent, an oil, or acombination thereof.

Embodiment 21 provides the method of any one of Embodiments 1-20,wherein the medium is an aqueous medium.

Embodiment 22 provides the method of Embodiment 21, wherein water is 50wt % to 100 wt % of the aqueous medium.

Embodiment 23 provides the method of any one of Embodiments 21-22,wherein water is 80 wt % to 100 wt % of the aqueous medium.

Embodiment 24 provides the method of any one of Embodiments 1-23,wherein the medium comprises liquid or gaseous effluent from acoal-fired electrical plant.

Embodiment 25 provides the method of any one of Embodiments 1-24,wherein the medium comprises flue gas from a coal-fired electricalplant, water from the coal-fired electrical plant, or a combinationthereof.

Embodiment 26 provides the method of any one of Embodiments 1-25,wherein the medium comprises a liquid used in or obtained from a miningoperation.

Embodiment 27 provides the method of any one of Embodiments 1-26,wherein the target material is 1 part per trillion to 50 wt % of theused CZTS sorbent.

Embodiment 28 provides the method of any one of Embodiments 1-27,wherein the target material is 0.0001 wt % to 20 wt/o of the used CZTSsorbent.

Embodiment 29 provides the method of any one of Embodiments 1-28,wherein the used CZTS sorbent comprises the target material absorbed onand/or in the CZTS sorbent, adsorbed and/or in the CZTS sorbent,complexed on and/or in the CZTS sorbent, amalgamed on and/or in the CZTSsorbent, or a combination thereof.

Embodiment 30 provides the method of any one of Embodiments 1-29,wherein the used CZTS sorbent comprises the target material in anunchanged chemical state as compared to the form of the target materialin the medium, as a complex, compound, or amalgam formed with the CZTSsorbent, or a combination thereof.

Embodiment 31 provides the method of any one of Embodiments 1-30,wherein the used CZTS sorbent comprises the target material as anamalgam formed with the CZTS sorbent.

Embodiment 32 provides the method of any one of Embodiments 2-31,wherein the target material is 1 part per trillion to 100 wt % of theextract.

Embodiment 33 provides the method of any one of Embodiments 2-32,wherein the target material is 0.001 wt % to 99.9 wt % of the extract.

Embodiment 34 provides the method of any one of Embodiments 2-33,wherein the extract comprises a liquid or gas used for the removing ofthe target material from the used CTZS sorbent, a derivative of a liquidor gas used for the removing of the target material from the used CTZSsorbent, or a combination thereof.

Embodiment 35 provides the method of any one of Embodiments 2-34,wherein the extract is substantially free of the CZTS sorbent and CZTS.

Embodiment 36 provides the method of any one of Embodiments 2-35,wherein the extract is substantially free of the medium.

Embodiment 37 provides the method of any one of Embodiments 1-36,wherein CZTS sorbent comprises a mixture comprising copper, zinc, tin,and sulfur.

Embodiment 38 provides the method of any one of Embodiments 1-37,wherein the CZTS sorbent comprises copper zinc tin sulfide having theformula Cu₂ZnSnS₄.

Embodiment 39 provides the method of any one of Embodiments 1-38,wherein the CZTS comprises ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or acombination thereof.

Embodiment 40 provides the method of any one of Embodiments 1-39,wherein CZTS is 0.001 wt % to 100 wt % of the CZTS sorbent.

Embodiment 41 provides the method of any one of Embodiments 1-40,wherein CZTS is 50 wt % to 100 wt % of the CZTS sorbent.

Embodiment 42 provides the method of any one of Embodiments 1-41,wherein the CZTS in the CZTS sorbent is unalloyed CZTS, an alloy ofCZTS, or a combination thereof.

Embodiment 43 provides the method of any one of Embodiments 1-42,wherein the CZTS sorbent comprises an element, metal, or compound inaddition to copper, zinc, tin, and sulfur.

Embodiment 44 provides the method of Embodiment 43, wherein the element,metal, or compound in the CZTS sorbent is comprised in the CZTS sorbentas a mixture, as an alloy, as a coating thereon, as a CZTS-coatedmaterial, or a combination thereof.

Embodiment 45 provides the method of any one of Embodiments 43-44,wherein the element, metal, or compound in the CZTS sorbent compriseszinc, iron, aluminum, sulfur, selenium, a selenite, ferrous oxide,ferric oxide, or a combination thereof.

Embodiment 46 provides the method of any one of Embodiments 43-45,wherein the element, metal, or compound in the CZTS sorbent comprises aclay, zeolite, a hydroxide salt, or a combination thereof.

Embodiment 47 provides the method of any one of Embodiments 43-46,wherein the element, metal, or compound in the CZTS sorbent comprisesbentonite, zeolite, calcium hydroxide, or a combination thereof.

Embodiment 48 provides the method of any one of Embodiments 43-47,wherein the element, metal, or compound in the CZTS sorbent is 0.001 wt% to 70 wt % of the CZTS sorbent.

Embodiment 49 provides the method of any one of Embodiments 1-48,wherein the CZTS sorbent comprises particulate CZTS, monolithic CZTS, aCZTS coating, a CTZS sheet, a CTZS film, or a combination thereof.

Embodiment 50 provides the method of any one of Embodiments 1-49,wherein the CZTS sorbent has a particle size of 0.5 nm to 3 inches.

Embodiment 51 provides the method of any one of Embodiments 1-50,wherein the CZTS sorbent has a particle size of 0.5 nm to 7,500 microns.

Embodiment 52 provides the method of any one of Embodiments 1-51,wherein the CZTS sorbent has a surface area of 0.2 m²/g to 2000 m²/g.

Embodiment 53 provides the method of any one of Embodiments 1-52,wherein the CZTS sorbent has a density of 2 to 8 g/cm³.

Embodiment 54 provides the method of any one of Embodiments 1-53,wherein the CZTS sorbent has a density of 4 to 5 g/cm³.

Embodiment 55 provides the method of any one of Embodiments 1-54,wherein the CZTS sorbent has a density of 4.5 to 4.6 g/cm³.

Embodiment 56 provides the method of any one of Embodiments 1-55,wherein the contacting comprises contacting the CZTS sorbent and themedium.

Embodiment 57 provides the method of any one of Embodiments 1-56,wherein the contacting comprises flowing the medium through a fixed bedcomprising the CZTS sorbent, flowing the medium through a columncomprising the CZTS sorbent, flowing the medium through an apparatuscomprising the CZTS sorbent deposited therein, suspending the CZTSsorbent in the medium, injecting the CZTS sorbent into the medium, or acombination thereof.

Embodiment 58 provides the method of any one of Embodiments 1-57,wherein the contacting comprises flowing the medium through areverse-venturi apparatus comprising the CZTS sorbent deposited therein.

Embodiment 59 provides the method of any one of Embodiments 1-58,wherein the contacting is performed at ambient temperature.

Embodiment 60 provides the method of any one of Embodiments 1-59,wherein the contacting is performed at a temperature of −100° C. to5,000° C.

Embodiment 61 provides the method of any one of Embodiments 1-60,wherein the contacting is performed at a temperature of 1° C. to 300° C.

Embodiment 62 provides the method of any one of Embodiments 1-61,wherein the contacting is performed for a duration of 30 d to 0.000001s.

Embodiment 63 provides the method of any one of Embodiments 1-62,wherein the contacting is performed for a duration of 1 h to 0.000001 s.

Embodiment 64 provides the method of any one of Embodiments 1-63,wherein the separating comprises removing the used CZTS sorbent from themedium, removing the medium from the used CZTS sorbent, or a combinationthereof.

Embodiment 65 provides the method of any one of Embodiments 1-64,wherein the separating comprises separating the used CZTS sorbent fromthe medium using a particulate separation device.

Embodiment 66 provides the method of Embodiment 65, wherein theparticulate separation device comprises a filter, an electrostaticprecipitator, a scrubber, or a combination thereof.

Embodiment 67 provides the method of any one of Embodiments 1-66,wherein the separating comprises filtering the used CZTS sorbent fromthe medium.

Embodiment 68 provides the method of any one of Embodiments 1-67,wherein the separating comprises replacing the medium comprising thetarget material with a different medium.

Embodiment 69 provides the method of any one of Embodiments 1-68,wherein the target material is about 0 wt % to 99.99 wt % of the mediumhaving the CZTS sorbent separated therefrom.

Embodiment 70 provides the method of any one of Embodiments 1-69,wherein the target material is about 0 wt % to 20 wt % of the mediumhaving the CZTS sorbent separated therefrom.

Embodiment 71 provides the method of any one of Embodiments 1-70,wherein the target material is 0 wt % to 5 wt % of the medium having theCZTS sorbent separated therefrom.

Embodiment 72 provides the method of any one of Embodiments 1-71,wherein the target material is about 0 wt % to 0.1 wt % of the mediumhaving the CZTS sorbent separated therefrom.

Embodiment 73 provides the method of any one of Embodiments 1-72,wherein the medium having the CZTS sorbent separated therefrom issubstantially free of the target material.

Embodiment 74 provides the method of any one of Embodiments 2-73,wherein the extract comprises a greater concentration of the targetmaterial than a concentration of the target material in the medium.

Embodiment 75 provides the method of any one of Embodiments 2-74,wherein the removing comprises heating the used CZTS sorbent, extractingthe target material from the used CZTS sorbent using liquid or gaseousextraction, dissolving the CZTS from the used CZTS sorbent,chemically-reacting the target material in the CZTS sorbent,chemically-reacting the CZTS in the used CZTS sorbent, or a combinationthereof.

Embodiment 76 provides the method of any one of Embodiments 2-75,wherein the removing comprises placing the used CZTS sorbent in a vacuumdrier.

Embodiment 77 provides the method of any one of Embodiments 2-76,wherein the removing comprises contacting the used CZTS sorbent with achemical reagent comprising an organic solvent, a fatty alcohol, alipid, a glycolipid, or a combination thereof, optionally as a mixturewith water.

Embodiment 78 provides the method of Embodiment 77, wherein the chemicalreagent comprises methanol, methyl ethyl ketone, methylene chlorine,glycerin, cetyl alcohol, stearyl alcohol, or a combination thereof,optionally as a mixture with water.

Embodiment 79 provides the method of any one of Embodiments 77-78,wherein the contacting of the used CZTS sorbent with the chemicalreagent is conducted at a pH of 6.49-9.05.

Embodiment 80 provides the method of any one of Embodiments 77-79,wherein the contacting of the used CZTS sorbent with the chemicalreagent is performed at 5 to 140° C.

Embodiment 81 provides the method of any one of Embodiments 77-80,wherein the contacting of the used CZTS sorbent with the chemicalreagent is performed at 85 to 110° C.

Embodiment 82 provides the method of any one of Embodiments 77-81,wherein the removing further comprises rinsing the used CZTS sorbentwith water or steam.

Embodiment 83 provides the method of any one of Embodiments 2-82,wherein the removing provides a recovered CTZS sorbent.

Embodiment 84 provides the method of Embodiment 83, further comprisingprocessing the recovered CZTS sorbent such that the recovered CZTSsorbent is effective for reuse in the method as the CTZS sorbent.

Embodiment 85 provides the method of any one of Embodiments 83-84,further comprising reusing the recovered CTZS sorbent in the method asthe CTZS sorbent.

Embodiment 86 provides a method of extracting a target material from amedium, the method comprising:

-   -   contacting a copper zinc tin sulfur (CZTS) sorbent with the        target material in the medium comprising the target material to        form a used CZTS sorbent that comprises the target material,        wherein the target material comprises mercury, a precious metal,        a rare earth metal, or a combination thereof;    -   separating the used CZTS sorbent from the medium; and    -   removing the target material from the used CZTS sorbent, to        obtain an extract comprising the target material.

Embodiment 87 provides a method of extracting a target material from amedium, the method comprising:

-   -   contacting a copper zinc tin sulfur (CZTS) sorbent with the        target material in the medium comprising the target material to        form a used CZTS sorbent that comprises the target material,        wherein the target material comprises a precious metal, a rare        earth metal, or a combination thereof, wherein the medium        comprises a liquid used in or obtained from a mining operation;    -   separating the used CZTS sorbent from the medium; and    -   removing the target material from the used CZTS sorbent, to        obtain an extract comprising the target material.

Embodiment 88 provides a method of extracting a target material from amedium, the method comprising:

-   -   contacting a copper zinc tin sulfur (CZTS) sorbent with the        target material in the medium comprising the target material to        form a used CZTS sorbent that comprises the target material,        wherein the target material comprises a polluting substance, a        toxic substance, a poisonous substance, or a combination        thereof, wherein the medium comprises flue gas from a coal-fired        electrical plant, water from the coal-fired electrical plant, or        a combination thereof;    -   separating the used CZTS sorbent from the medium; and    -   removing the target material from the used CZTS sorbent, to        obtain an extract comprising the target material.

Embodiment 89 provides a method of forming a CZTS sorbent, the methodcomprising:

-   -   combining        -   copper, a compound thereof, or a salt thereof,        -   zinc, a compound thereof, or a salt thereof,        -   tin, a compound thereof, or a salt thereof, and        -   sulfur, a compound thereof, or a salt thereof,    -   to form a starting material mixture; and    -   processing the starting material mixture under conditions        suitable to form the CZTS sorbent.

Embodiment 90 provides the method of Embodiment 89, wherein theprocessing comprises mixing the starting material mixture.

Embodiment 91 provides the method of any one of Embodiments 89-90,wherein the processing comprises heating the starting material mixture.

Embodiment 92 provides the method of any one or any combination ofEmbodiments optionally configured such that all elements or optionsrecited are available to use or select from.

What is claimed is:
 1. A method of extracting a target material from amedium, the method comprising: contacting a copper zinc tin sulfur(CZTS) sorbent with the target material in the medium comprising thetarget material to form a used CZTS sorbent that comprises the targetmaterial; and separating the used CZTS sorbent from the medium.
 2. Themethod of claim 1, further comprising removing the target material fromthe used CZTS sorbent, to obtain an extract comprising the targetmaterial.
 3. The method of claim 1, wherein the target materialcomprises a metal, a heavy metal, a precious metal, a rare earth metal,sulfur, nitrogen, nitrogen dioxide, a nitrate, phosphorus, a phosphate,sulfur, sulfur dioxide, ammonia, boron, a compound thereof, a complexthereof, a salt thereof, an organic solvent, or a combination thereof.4. The method of claim 1, wherein the target material comprises aprecious metal.
 5. The method of claim 1, wherein the target materialcomprises a coinage group metal, a platinum group metal, or acombination thereof.
 6. The method of claim 1, wherein the targetmaterial comprises a polluting substance, a toxic substance, a poisonoussubstance, or a combination thereof.
 7. The method of claim 1, whereinthe target material is mercury, an oxide thereof, or a combinationthereof.
 8. The method of claim 1, wherein the medium comprises liquid,gas, or a combination thereof.
 9. The method of claim 1, wherein themedium comprises water, an organic solvent, an oil, or a combinationthereof.
 10. The method of claim 1, wherein the medium comprises liquidor gaseous effluent from a coal-fired electrical plant, a medium used inor obtained from a mining operation, or a combination thereof.
 11. Themethod of claim 1, wherein the used CZTS sorbent comprises the targetmaterial absorbed on and/or in the CZTS sorbent, adsorbed and/or in theCZTS sorbent, complexed on and/or in the CZTS sorbent, amalgamed onand/or in the CZTS sorbent, or a combination thereof.
 12. The method ofclaim 1, wherein the CZTS sorbent comprises copper zinc tin sulfidehaving the formula Cu₂ZnSnS₄.
 13. The method of claim 1, wherein theCZTS sorbent comprises ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combinationthereof.
 14. The method of claim 1, wherein the CZTS sorbent comprisesan element, metal, or compound in addition to copper, zinc, tin, andsulfur.
 15. The method of claim 1, wherein the CZTS sorbent comprisesparticulate CZTS, monolithic CZTS, a CZTS coating, a CTZS sheet, a CTZSfilm, or a combination thereof.
 16. The method of claim 1, wherein thecontacting comprises flowing the medium through a fixed bed comprisingthe CZTS sorbent, flowing the medium through a column comprising theCZTS sorbent, flowing the medium through an apparatus comprising theCZTS sorbent deposited therein, suspending the CZTS sorbent in themedium, injecting the CZTS sorbent into the medium, or a combinationthereof.
 17. The method of claim 1, wherein the separating comprisesseparating the used CZTS sorbent from the medium using a particulateseparation device.
 18. The method of claim 2, wherein the extract isenriched in the target material relative to the medium comprising thetarget material prior to the contacting with the CZTS sorbent.
 19. Themethod of claim 2, wherein the removing comprises heating the used CZTSsorbent, extracting the target material from the used CZTS sorbent usingliquid or gaseous extraction, dissolving the CZTS from the used CZTSsorbent, chemically-reacting the target material in the CZTS sorbent,chemically-reacting the CZTS in the used CZTS sorbent, or a combinationthereof.
 20. The method of claim 2, wherein the removing comprisesplacing the used CZTS sorbent in a vacuum drier; or contacting the usedCZTS sorbent with a chemical reagent comprising an organic solvent, afatty alcohol, a lipid, a glycolipid, or a combination thereof,optionally as a mixture with water; or a combination thereof.
 21. Themethod of claim 2, wherein the removing provides a recovered CTZSsorbent, further comprising reusing the recovered CTZS sorbent in themethod as the CTZS sorbent.
 22. A method of extracting a target materialfrom a medium, the method comprising: contacting a copper zinc tinsulfur (CZTS) sorbent that comprises Cu₂ZnSnS₄ with the target materialin the medium comprising the target material to form a used CZTS sorbentthat comprises the target material, wherein the target materialcomprises a precious metal, a rare earth metal, or a combinationthereof, wherein the medium comprises a liquid used in or obtained froma mining operation; separating the used CZTS sorbent from the medium;and removing the target material from the used CZTS sorbent, to obtainan extract comprising the target material.
 23. A method of extracting atarget material from a medium, the method comprising: contacting acopper zinc tin sulfur (CZTS) sorbent that comprises Cu₂ZnSnS₄ with thetarget material in the medium comprising the target material to form aused CZTS sorbent that comprises the target material, wherein the targetmaterial comprises a polluting substance, a toxic substance, a poisonoussubstance, or a combination thereof, wherein the medium comprises fluegas from a coal-fired electrical plant, water from the coal-firedelectrical plant, or a combination thereof; separating the used CZTSsorbent from the medium; and removing the target material from the usedCZTS sorbent, to obtain an extract comprising the target material.
 24. Amethod of forming a CZTS sorbent, the method comprising: combiningcopper, a compound thereof, or a salt thereof, zinc, a compound thereof,or a salt thereof, tin, a compound thereof, or a salt thereof, andsulfur, a compound thereof, or a salt thereof, to form a startingmaterial mixture; and processing the starting material mixture underconditions suitable to form the CZTS sorbent that comprises thatcomprises Cu₂ZnSnS₄.